synthesis of 1,3,5-triaza-7-phosphaadamantane...
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SYNTHESIS OF 1,3,5-TRIAZA-7-PHOSPHAADAMANTANE (PTA) AND 3,7-
DIACETYL-1,3,7-TRIAZA-5-PHOSPHABICYCLO[3.3.1]NONANE (DAPTA)
COMPLEXES AND THE DEVELOPMENT OF CHROMIUM SALEN
CATALYSTS FOR THE COPOLYMERIZATION OF CO2 AND EPOXIDES
A Dissertation
by
CESAR GABRIEL ORTIZ
Submitted to the Office of Graduate Studies of Texas A&M University
in partial fulfillment of the requirements for the degree of
DOCTOR OF PHILOSOPHY
May 2004
Major Subject: Chemistry
SYNTHESIS OF 1,3,5-TRIAZA-7-PHOSPHAADAMANTANE (PTA) AND 3,7-
DIACETYL-1,3,7-TRIAZA-5-PHOSPHABICYCLO[3.3.1]NONANE (DAPTA)
COMPLEXES AND THE DEVELOPMENT OF CHROMIUM SALEN
CATALYSTS FOR THE COPOLYMERIZATION OF CO2 AND EPOXIDES
A Dissertation
by
CESAR GABRIEL ORTIZ
Submitted to Texas A&M University
in partial fulfillment of the requirements for the degree of
DOCTOR OF PHILOSOPHY
Approved as to style and content by: ________________________ ________________________ Donald J. Darensbourg Marcetta Y. Darensbourg (Chair of Committee) (Member) ________________________ ________________________ Michael B. Hall Stephen A. Miller
(Member) (Member) ________________________ ________________________
Edward D. Harris Emile A. Schweikert (Member) (Head of Department)
May 2004
Major Subject: Chemistry
iii
ABSTRACT
Synthesis of 1,3,5-triaza-7-phosphaadamantane (PTA) and 3,7-diacetyl-1,3,7-triaza-5-
phosphabicyclo[3.3.1]nonane (DAPTA) Complexes and the Development of Chromium
Salen Catalysts for the Copolymerization of CO2 and Epoxides.
(May 2004)
Cesar Gabriel Ortiz, B.S., Baylor University
Chair of Advisory Committee: Dr. Donald J. Darensbourg
Two main areas are considered in this manuscript. The first describes the synthesis
of group 10 metal complexes incorporating the water-soluble 1,3,5-triaza-7-
phosphaadamantane (PTA) ligand and the second deals with the preparation of
Cr(salen)X catalysts for the copolymerization of CO2 and epoxides. In the first topic,
the synthesis of nickel(II) and palladium(II) salicylaldiminato complexes incorporating
PTA has been achieved employing two preparative routes. Upon reacting the original
ethylene polymerization catalyst developed by Grubbs and coworkers (Organometallics,
1998, 17, 3149), (salicylaldiminato)Ni(Ph)PPh3, with PTA using a homogeneous
methanol/toluene solvent system resulted in the formation of the PTA analogs in good
yields. Alternatively, complexes of this type may be synthesized via a direct approach
utilizing (TMEDA)M(CH3)2 (M = Ni, Pd), the corresponding salicylaldimine, and PTA.
Polymerization reactions were attempted using the nickel-PTA complexes in a biphasic
toluene/water mixture in an effort to initiate ethylene polymerization by trapping the
dissociated phosphine ligand in the water layer, thereby, eliminating the need for a
iv
phosphine scavenger. Unfortunately, because of the strong binding ability of the small,
donating phosphine (PTA) as compared to PPh3, dissociation did not occur at a
temperature where the complexes are not subjected to decomposition.
Additionally, the unexplored PTA derivative, 3,7-diacetyl-1,3,7-triaza-5-
phosphabicyclo[3.3.1]nonane (DAPTA), prepared by the literature procedure, was fully
characterized by NMR and X-ray analysis. DAPTA is found be similar to its parent
(PTA) in coordination mode and binding strength, as supported by its representative
group 6 and group 10 complexes
The second main topic involves the copolymerization of CO2 and epoxides (i.e.,
cyclohexene oxide (CHO)) for the formation of polycarbonate using Cr(salen)X (X = Br,
OPh) catalysts with one equivalent of PR3 as the co-catalyst. The use of these catalysts
and cocatalysts results in the most active chromium-based catalytic systems to date. The
highest activities observed are on the order of 109 mol CHO consumed . mol Cr-1 . hr-1
using PCy3 as the co-catalyst, and is clearly seen in the in situ monitoring of copolymer
formation. An advantage of these systems involves the lack of cyclic carbonate
production and high CO2 incorporation (>99%) within the polymer.
v
DEDICATION
This dissertation is dedicated to my wife, Diana Alicia Ortiz.
Durante el curso de mis estudios posgrado, solamente hay un recuerdo que me ha
hecho sentir sinceramente feliz y por el, he cumplido con mi carera. El evento se realizo
el 23 de Diciembre del año 2000. En esta fecha no unimos, casados para siempre. Tu
apoyo y mas que nada, tu fe en mi durante estos cinco años es lo que me ha impulsado
para lograr algo que nunca se hubiera realizado. Gracias corazon por tus consejos y fe
en tu esposo; por tus sonrisas, comentarios, amistad, y cariño durante los dias que se
hacian eternos en el laboratorio. Gracias Diana, mi amor.
vi
ACKNOWLEDGEMENTS
At the end of my undergraduate career at Baylor University, the most valuable
advice given to me concerned the balance between choosing the chemistry that I was to
undertake and selecting a graduate advisor in graduate school. Without a doubt, the
most important part of this advice is the latter since I have tremendously enjoyed
working under the direction of Dr. Donald J. Darensbourg. He has provided me with the
opportunity to develop the thoughts and skills necessary for the next step in my career.
Thank you, Don, not only for the chemistry related dialogues, but also for the everyday
conversations that have contributed to a great stay at Texas A&M University. I would
also like to thank Dr. Denise T. Magnuson for her wonderful introduction of chemistry
at Baylor University, which I tremendously enjoyed and still remember. I would like to
thank Dr. Carlos Manzanares at Baylor University, who taught me invaluable concepts
and provided a rewarding laboratory experience. In addition, I would also like to thank
Dr. Kevin Burgess for providing me with my first research graduate experience and Dr.
Armin A. Burghart for his mentoring during this 1999 summer period. To be thanked as
well are my committee members, Dr. Marcetta Darensbourg, Dr. Michael Hall, Dr.
Stephen Miller, Dr. Edward Harris, and Dr. Siegfried Musser (for serving as my GCR
during preliminary exams) for their time and suggestions.
I would also like to thank Dr. Joseph Reibenspies for his assistance with crystal
structure data, and his willingness to help with any data acquisition question. Further
people to thank are the MYD and DJD group members. Specifically, I would like to
thank Jody Rodgers for the good times spent in and out of the lab: thanks bud. Other
vii
people that I would like to thank are Dr. Jacob Wildeson, Dr. Jason Yarbrough, Dr.
Jason Adams, Dr. Sam Lewis, Ryan Mackiewicz, Damon Billodeaux, Andrea Phelps,
and Sue Winters: All of you "rock out." I sincerely enjoyed all the great conversations,
and will always remember all of you. Thank you, Sue, for all of your help with
everyday questions. Work was never a dull moment with all of you guys.
Finally, I would like to thank my parents, Gabriel and Hermelinda Ortiz, for their
support during my undergraduate and graduate studies. Thank you for showing us the
way to success heavily depends on hard work, loyalty, and respect. What you have
instilled in me will always be remembered and passed on.
viii
TABLE OF CONTENTS
Page
ABSTRACT .............................................................................................................. iii DEDICATION .......................................................................................................... v ACKNOWLEDGEMENTS ...................................................................................... vi TABLE OF CONTENTS .......................................................................................... viii LIST OF FIGURES................................................................................................... xi LIST OF TABLES .................................................................................................... xv CHAPTER I INTRODUCTION............................................................................. 1 II SYNTHESIS OF NICKEL AND PALLADIUM SALICYLALDIMINATO 1,3,5-TRIAZA-7- PHOSPHAADAMANTANE (PTA)COMPLEXES ......................... 17 Introduction ........................................................................... 17 Experimental ......................................................................... 22 Results and Discussion.......................................................... 30 Concluding Remarks ............................................................. 53 III SYNTHESIS AND CHARACTERIZATION OF 3,7-DIACETYL-1,3,7-TRIAZA-5-PHOSPHABICYCLO[3.3.1] NONANE (DAPTA) AND ITS GROUP 6 AND GROUP 10 COMPLEXES ................................................................................... 57 Introduction ........................................................................... 57 Experimental ......................................................................... 60 Results and Discussion.......................................................... 65 Concluding Remarks ............................................................. 85
ix
TABLE OF CONTENTS (CONTINUED)
CHAPTER Page
IV DEVELOPMENT OF NOVEL CHROMIUM SALEN CATALYSTS FOR THE COPOLYMERIZATION OF CO2 AND EPOXIDES................................................................ 87 Introduction ........................................................................... 87 Experimental ......................................................................... 90 Results and Discussion.......................................................... 95 Concluding Remarks ............................................................. 117 V SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF IRON(III) SALEN COMPLEXES POSSESSING ANIONIC OXYGEN DONOR LIGANDS ........................................................ 121 Introduction ........................................................................... 121 Experimental ......................................................................... 124 Results and Discussion.......................................................... 126 Concluding Remarks ............................................................. 138 VI METHYLATION REACTIONS OF GROUP 10 1,3,5-TRIAZA-7-PHOSPHOAADAMANTANE COMPLEXES USING CH3OSO2F AND SYNTHESIS OF NOVEL PALLADIUM-NICKEL DACO TRIMERS ...................... 140 Introduction ........................................................................... 140 Experimental ......................................................................... 143 Results and Discussion.......................................................... 146 Concluding Remarks ............................................................. 161 VII CONCLUSIONS............................................................................... 166 REFERENCES.......................................................................................................... 172 APPENDIX A ........................................................................................................... 182 APPENDIX B ........................................................................................................... 213
x
TABLE OF CONTENTS (CONTINUED)
Page APPENDIX C ........................................................................................................... 220 APPENDIX D ........................................................................................................... 244 APPENDIX E............................................................................................................ 255 VITA ......................................................................................................................... 268
xi
LIST OF FIGURES
FIGURE Page
1.1 Late-transition metal catalysts for the polymerization of olefins in aqueous media.................................................................. 3
1.2 Representative examples of WSP for use in aqueous organometallic catalysis ....................................................................... 6 1.3 Homogeneous zinc-based catalysts for the copolymerization of CO2 and epoxides............................................................................. 10 1.4 Chromium-based catalysts for the copolymerization of CO2 and epoxides ......................................................................................... 14 1.5 Spacial orientation of nucleophile relative to substrate binding site ........................................................................................... 15 2.1 Salicylaldiminato nickel(II) catalyst .................................................... 19 2.2 Examples of WSP used in aqueous catalysis ....................................... 21 2.3 Thermal ellipsoid representation of trans-(PPh3)2NiCl(Ph) showing 50% probability ..................................................................... 32 2.4 Representative 1H NMR spectrum of Pd(1/2Sal-Cl)PTA, 4d.............. 35 2.5 Thermal ellipsoid representation of Ni(1/2Sal-NO2)PPh3, 1a, showing 50% probability ............................................................... 41 2.6 Thermal ellipsoid representation of Ni(1/2Sal-NO2)PTA, 2a, showing 50% probability ............................................................... 43 2.7 Thermal ellipsoid representation of Pd(1/2Sal-NO2)PTA, 4a, showing 50% probability ............................................................... 44 2.8 Thermal ellipsoid representation of Pd(1/2Sal-OMe)PTA, 4b, showing 50% probability ............................................................... 46
xii
LIST OF FIGURES (CONTINUED) FIGURE Page
2.9 Thermal ellipsoid representation of Ni(1/2Sal-OMe)PTA, 3b, showing 50% probability ............................................................... 47 2.10 Thermal ellipsoid representation of Ni(1/2Sal-Cl)PTA, 3d, showing 50% probability ............................................................... 48 2.11 Thermal ellipsoid representation of Pd(1/2Sal-Ben)PTA, 4c, showing 50% probability................................................................ 49 2.12 Thermal ellipsoid representation of Pd(1/2Sal-Cl)PTA, 4d, showing 50% probability ............................................................... 50 2.13 Thermal ellipsoid representation of Ni(1/2Sal-OMe)2, 3b', showing 50% probability .............................................................. 51 2.14 Polymerization of ethylene using 3/4 in a biphasic toluene/water solvent system ...................................................................................... 52 2.15 Thermal ellipsoid representation of Pd(1/2Sal-Cl)DAPTA, 4d-DAPTA, showing 50% probability ................................................ 56 3.1 Examples of water-soluble phosphines ................................................ 59 3.2 Molar water-solubility of selected tertiary water-soluble phosphines............................................................................................ 67 3.3 Thermal ellipsoid representation of DAPTA (1) showing 50% probability ............................................................................................ 72 3.4 Space filling model of DAPTA (1) showing (a) front and (b) side view......................................................................................... 74 3.5 Shielding effects on geminal protons by acyl groups in DATPA oxide (2) ................................................................................. 75 3.6 Thermal ellipsoid representation of DAPTA oxide (2) showing 50% probability ..................................................................... 76
xiii
LIST OF FIGURES (CONTINUED)
FIGURE Page
3.7 Space filling model of DAPTA oxide (2) showing (a) front and (b) side view .................................................................................. 78 3.8 Thermal ellipsoid representation of W(CO)5(DAPTA) (5) showing 50% probability................................................................ 83 3.9 Thermal ellipsoid representation of Cr(CO)5(DAPTA) (6) showing 50% probability................................................................ 84 4.1 Jacobsen's initiation step ...................................................................... 89 4.2 Cr(salen)X catalysts for the copolymerization of CO2 and epoxides ......................................................................................... 91 4.3 Thermal ellipsoid representation of Cr(salen)(Br)(THF), 2.THF, showing 50% probability......................................................... 102 4.4 Thermal ellipsoid representation of Cr(salen)(Br)(CH3CN), 2.CH3CN, showing 50% probability.................................................... 103 4.5 Thermal ellipsoid representation of [Cr(salen)(OPBu3)]+[Br]-, 2.2OPBu3, showing 50% probability ................................................... 104 4.6 Three dimensional plot of copolymer growth at 1750 cm-1 using Cr(salen)Br, 1, with one equivalent of PCy3 .............................. 107 4.7 Trace of 1750 cm-1 copolymer growth using several different phosphines with Cr(salen)Br, 1, as the cocatalyst................................ 109 4.8 1H NMR of CO2/PO/TMSO terpolymer using Cr(salen)Br, 1, as the catalyst with one equivalent of PCy3 ......................... 112 4.9 Thermal ellipsoid representation of Cr(1/2Sal)2(CH3CN)(Cl), 7a, showing 50% probability .............................................................. 115
xiv
LIST OF FIGURES (CONTINUED) FIGURE Page
4.10 Ball and stick representation of Cr(1/2Sal)2(Cl)(N-MeIm).................. 116 4.11 Thermal ellipsoid representation of [Cr(1/2Sal)2(Cl)]2, 8, showing 50% probability ................................................................. 118 4.12 Initiation step involving Cr(salen)X catalysts, 1-4, with PR3 activation ....................................................................... 119 5.1 Fe(salen)X complexes incorporating monodentate and bidentate anionic ligands...................................................................... 123 5.2 Thermal ellipsoid representation of Fe(salen)(OPh) (1) showing 50% probability .................................................................................... 132 5.3 Thermal ellipsoid representation of Fe(salen)(acac) (2) showing 50% probability .................................................................................... 135 5.4 Thermal ellipsoid representation of µ-[Fe(salen)]2O (3) showing 50% probability .................................................................................... 137 6.1 Active site in the A cluster of Acetyl CoA Synthase ........................... 140 6.2 Thermal ellipsoid representation of Pt[(PTA-CH3
+)(OSO2F-)]4
(5) showing 50% probability................................................................ 152 6.3 Thermal ellipsoid representation of Pt[(PTA-CH3
+)(I-)]4
(7) showing 50% probability................................................................ 154 6.4 Thermal ellipsoid representation of (BME-DACO)Ni-Pd(CH3)(Cl) (8') showing 50% probability............................................................... 158 6.5 Thermal ellipsoid representation of [(BME-DACH)Ni]2-[Pd(CH3)]2(OPh) (9) showing 50% probability ............................................................................................ 160 6.6 Selected plane angles of complex [(BME-DACH)Ni]2-[Pd(CH3)]2(OPh) (9) ........................................... 162 6.7 Holm's Ni(bpy)(CH3)(SR) complex ..................................................... 164
xv
LIST OF TABLES
TABLE Page
2.1 Crystallographic data for complex trans-(PPh3)2NiCl(Ph)................. 30 2.2 Selected bond distances (Å) and angles for complex trans-(PPh3)2Ni(Cl)(Ph)...................................................................... 31 2.3 Crystallographic data for complexes 1a, 2a, 4a, 4b, 3b', 3b, 3d, 4c, 4d, and 4d-DAPTA........................................................................ 37 2.4 Selected bond distances (Å) and angles of complexes 1a, 2a, 4a, 4b, 3b', 3b, 3d, 4c, 4d, and 4d-DAPTA ........................................ 39 3.1 Crystallographic data for compounds 1, 2, 5, and 6............................. 69 3.2 Selected bond distances (Å) and angles for compounds 1, 2, 5, and 6 ......................................................................................... 70 4.1 Crystallographic data and data collection parameters for 2.THF, 2.CH3CN, 2.2OPBu3, 7a, and 8 .............................................. 97 4.2 Selected bond distances (Å) and angles for complexes 2.THF, 2.CH3CN, 2.2OPBu3, 7a, and 8 .............................................. 98 4.3 Activities associated with the use of catalysts 1-4 along with one equivalent of cocatalyst ................................................................. 105 4.4 Maximum rates and induction periods in the copolymerization of CO2 and epoxides using 1 as the catalyst......................................... 108 5.1 Crystallographic data and data collection parameters for complexes 1, 2, and 3 ........................................................................... 129 5.2 Selected bond distances (Å) and angles for complexes 1, 2, and 3 ............................................................................................. 130 6.1 Crystallographic data and data collection parameters for compounds 5, 7, 8', and 9..................................................................... 149 6.2 Selected bond distances (Å) and angles for compounds 5, 7, 8', and 9 ........................................................................................ 150
1
CHAPTER I
INTRODUCTION
The use of water as a suitable medium for catalysis has received much attention
in recent years.1 The increasing interest in this field stems from obvious economic and
safety considerations. That is, or specifically, replacing flammable, carcinogenic, and
explosive organic solvents with water leads to a safer working environment. From an
industrial point of view, an aqueous medium translates into waste reduction costs as well
as potentially recovering the catalysts via a biphasic process. The latter process is the
foundation of the Ruhrchemie-Rhône Poulenc hydroformylation of alkenes, where in
1998, it was reported to produce approximately 10% of the world’s C4-C5 aldehyde
capacity.1,2
Catalytic processes taking advantage of this benign medium include carbon-
carbon coupling (e.g., Heck, Suzuki, and Sonagoshira coupling), hydroformylation, and
hydrogenation reactions.1 However, only a small amount of work has been conducted in
the area of transition metal mediated polymerization of olefins in water.3 Currently, the
polymerization of most α-olefins depends heavily on Ziegler-Natta and metallocene
catalysts which are usually based on early transition metals to afford high molecular
weight polymer.4 Although very effective, they are extremely oxophilic and monomer
feeds must be purified prior to usage. Consequently, increasing attention is being given
_______________
This dissertation follows the style of the Journal of the American Chemical Society.
2
to late transition metals due to their lower oxophilicity and their ability to tolerate
functionalized olefins such as acrylates.5 The polymerization of such functionalized
monomers is of great interest due to the potential of producing adhesive polymeric
materials. Recently, several systems have appeared which utilize water as the solvent.
For example, Brookhart’s cationic β-diimine palladium catalyst was found to produce
high molecular weight, branched polyethylene in water (Figure 1.1).6 Furthermore,
activities are similar to those observed utilizing organic solvents (e.g., CH2Cl2). The
stable nature of the catalysts during polymerization is due to an “encapsulation” of the
hydrophobic catalyst by the growing polymer chain. Attempts to produce a truly
homogeneous water-soluble catalysts by the addition of sulfonated groups to the ligand
framework resulted in decomposition upon the introduction of ethylene.7 Other catalytic
systems include Mecking’s SHOP analog, which was found to produce polyethylene
with turnover numbers (TON) and polydispersities (PDI) on the order of 103 and 2-3,
respectively, in an aqueous medium (Figure 1.1).8
Of prime interest to our research is the nickel (II) salicylaldiminato catalyst,
developed by Grubbs and coworkers in 1998 (Figure 1.1).9 One of the major
advantages of this system involves the neutral nature of the active species, as no bulky
counterions are present during polymerization. In typical organic solvents (i.e., toluene),
the catalyst’s activity is comparable to traditional Ziegler-Natta and metallocene
catalysts. For example, activities as high as 6.40 x 106 g PE . mol Ni-1 . hr-1 were
obtained in the polymerization of ethylene. Using functionalized alkenes incorporating
3
Figure 1.1. Late-transition metal catalysts for the polymerization of olefins in aqueous media.
N
N
Pd
CH3
NCCH3
+SbF6
-
O
-O3S P
Ni
Ph
PPh3
Ph Ph
R1R2
R3
R4
O
Ni
N
L
R i-Pr
i-Pr
R = AlkylL = PR3, Pyridine, CH3CN
M+
Brookhart Mecking Grubbs
4
ketone, ether, and hydroxyl groups in the copolymerization with ethylene led to no
appreciable decrease in activity when compared to homopolymerization. To further
illustrate the stability of the catalysts, water was added to the reaction mixture and was
found to only slightly affect the production of polyethylene. The polymerization of
ethylene in water as the solvent using this catalyst has been reported.8 High molecular
weight polymer was obtained with TON’s on the order of 9.22 x 103 mol ethylene
consumed . mol Ni-1. Furthermore, using surfactants to create miniemulsions resulted in
the production of stable polyethylene latex particles.10
In order to achieve high TON’s, electron withdrawing groups on the
salicylaldimine ligand framework are necessary, rendering a more electron deficient
metal center. The drawback, however, as is the case for many other catalytic systems,
involves the need for a phosphine scavenger ([PS]) or a co-catalyst to allow the
formation of the active species for many of these derivatives (Scheme 1.1).
Scheme 1.1
O
Ni
N
L
R
[PS]
[PS]- L
O
Ni
N R
O
Ni
N R
Typically, these [PS] are highly air sensitive and are not economically feasible, making
them impractical from an industrial point of view.
Utilization of a biphasic organic/water medium in conjunction with replacing the
hydrophobic triphenylphosphine (L) with a water soluble phosphine (WSP) may lead to
5
the irreversible dissociation of the WSP into the aqueous phase. Through the years,
many WSP’s have appeared, from sulfonated aryl derivatives to carboxylic or nitrogen-
containing species. A prime example is the use of the tri-sulfonated triphenylphosphine
derivative, TPPTS, in the aforementioned Ruhrchemie-Rhône Poulenc process (Figure
1.2).1,2 However, of interest to this work is the heterocyclic aliphatic 1,3,5-triaza-7-
phosphaadamantane (PTA) ligand (Figure 1.2).11 Much research has been conducted in
the area of hydrogenation of unsaturated substrates using rhodium and ruthenium
complexes of PTA, but little attention has been given to the catalytic properties of group
10 PTA complexes.12 Catalysts employing TPPTS as the WSP have appeared through
the years for carbon-carbon coupling reactions1, but the use of Pd(PTA)413 in the Heck
reaction of terminal alkenes with aryl iodides has yet to be studied (eq. 1.1).
(1.1)
Additionally, there is considerable interest in the derivitation of PTA to afford other
WSP’s and their respective water-soluble group 10 complexes. For example,
methylation and acylation of PTA affords 1-methyl-1-azonia-3,5-diaza-7-
phosphaadamantane (PTA-CH3+)(I-)11a and 3,7-diacetyl-1,3,7-triaza-5-
phosphabicyclo[3.3.1]nonane (DAPTA)11d, respectively (Figure 1.2). The former
R
X
+
R'
R
R'
[catalyst]
6
Figure 1.2. Representative examples of WSP for use in aqueous organometallic catalysis.
N NN
P
N NN
P
O
O
P
SO3- M+SO3
- M+
SO3- M+
PTA
DAPTA
TPPTS
N NN
P
H3C I-
(PTA-CH3+)(I-)
M=Na+, K+,...
7
derivative has been studied to a greater extent, as rhodium complexes have been found to
be moderate catalysts in the hydrogenation of unsaturated substrates14. However, the
physical properties of DAPTA and its complexes remain unexplored.
It is the purpose of the studies presented herein to address the following issues: (1)
Can a WSP’s, such as PTA, be incorporated into group 10 (M = Ni, Pd)
salicylaldiminato complexes, and (2) will these derivatives be active towards the
polymerization of ethylene utilizing a biphasic aqueous/organic medium? (3) Can other
derivatives be made using the same synthetic methodology bearing different WSP’s
(e.g., DAPTA)? This work and their findings should create a new avenue for the
formation of active catalytic species without the need of a co-catalyst for this and other
related polymerization processes.
Furthermore, other issues related to aqueous organometallic catalysis are addressed:
(4) What are the physical properties of the acylated PTA analog, DAPTA? (5) How does
the electron donating ability of DAPTA compare to PTA by examining crystal data and
v(CO) stretching frequencies of group 6 carbonyl derivatives? (6) Can methylation at
the metal center of group 10 metal PTA complexes (e.g., Ni(PTA)4) with a strong
methylating agent be achieved? The findings of these studies should provide insight into
bioinorganic catalytic systems and add another potential ligand to the array of WSPs
available for possible use in aqueous organometallic chemistry.
Apart from aqueous polymerization and carbon-carbon bond formation reactions
using WSP’s, there has been great interest in the area of transition metal mediated
copolymerization of CO2 and epoxides for the production of polycarbonates.15 Through
8
the years, the need for new polymeric materials to suit a variety of applications has been
on the rise. With this in mind, polycarbonates exhibit many favorable physical
properties such as toughness, clarity, and thermal stability.16 These favorable attributes
make the copolymer ideal for applications such as optical lenses, CD’s, DVD’s,
automotive parts, along with many others.
Currently, the copolymer is made by the interfacial condensation of diols, such as
bisphenol-A, and phosgene in an aqueous/chlorinated hydrocarbon reaction medium
(e.g., methylene chloride). The reaction is carried out by introducing phosgene to an
aqueous alkali solution of bisphenol-A (eq. 1.2).
OHHO
+
Cl
O
Cl
NaOHCH2Cl2
O
O
O n
+ 2n NaCl
(1.2) The major disadvantage associated with this process concerns the high toxicity of both
monomers, which translates into higher production costs, and is the impetus for the
development of an alternate environmentally benign process.
9
The synthesis of polycarbonates via a transition metal catalyzed route was first
envisioned by Shohei Inoue in Japan.17 In 1969, he reported the copolymerization of
CO2 with aliphatic epoxides. The utilization of CO2 as a C1 feedstock is of great
importance in chemical transformations, and many reactions have been developed for
the specific use of this small stable molecule.18 Inoue’s catalytic system was prepared
by the reaction of diethyl zinc with one equivalent of water, forming an insoluble zinc
aggregate (eq. 1.3).
(1.3) Although the production of high molecular weight polycarbonate was achieved, the yield
was poor, and the reaction was plagued by reproducibility issues and required large
catalyst loadings.
In the following years, other heterogeneous catalytic systems were developed using
this methodology by reacting a variety of protonated substrates (e.g., primary amines,
diols, dicarboxylic acids) with diethyl zinc.19 The metal center was also varied as
aluminum, chromium, cobalt, and nickel were used with limited success.20 The
heterogeneous nature of these early catalysts prompted the need for a more well-
characterized catalyst.
The most active system was first developed by Darensbourg and co-workers with
the use of a zinc-based catalyst, Zn(OAr)2, where OAr represents a variety of sterically
encumbered phenoxides (Figure 1.3).21 Depending on the exact nature of the phenoxide,
n Zn(C2H5)2 + n H2O C2H5__Zn__O_Zn__
n-1__OH
- (2n-1) C2H6
10
Darensbourg Coates
Figure 1.3. Homogeneous zinc-based catalysts for the copolymerization of CO2 and epoxides.
11
it was demonstrated to be a suitable nucleophile to either insert CO2 or ring open the
epoxide in the initiation step. TON’s and TOF’s were on the order of 1441 g polymer . g
Zn-1 and 21 g polymer . g Zn-1 . hr-1 (24 hr reaction), respectively, for the most active
species in the copolymerization of CO2 and cyclohexene oxide (CHO). In the late
1990’s, however, Coates and coworkers developed a series of zinc catalysts
incorporating a β-diimine ligand framework (Figure 1.3).22 This system is currently the
most attractive catalytic system for this process as high TON and TOF are obtained
under very mild reaction conditions. For example, in the copolymerization of CO2 and
CHO, one of the most active derivatives demonstrated a TON and TOF of 382 mol CHO
consumed . mol Zn-1 and 2290 mol CHO consumed . mol Zn-1 . hr-1 , respectively, under
a CO2 pressure of 100 psi at 50 ºC for a 10 minute reaction period. The copolymer
exhibited 90% carbonate linkages, but can be increased by raising the CO2 pressure to
800 psi.
The copolymerization of CO2 and epoxides using the aforementioned catalysts is
thought to occur via a coordinative anionic insertion process, and although Coates has
recently proposed a dimeric process for the β-diimine zinc catalyst, a simplified version
of his mechanism that may apply to the zinc phenoxide work is presented (Scheme
1.2).15b Step 1 involves the coordination of the epoxide to zinc (at an open site
accessible to the nucleophile) followed by nucleophilic ring opening at the least
sterically encumbering and/or more positively charged carbon on the epoxide. This is
followed by CO2 insertion (step 2) which generates the carbonate functionality. A
12
Scheme 1.2
LnZn OR +O
R1 R2 LnZn OR
O
R1R2
: :
STEP 1
LnZn O
R2R1
OR
CO2 Insertion
LnZnO
O
O
R2R1
OR
STEP 2
CO2 Insertion
O
R1 R2
[Zn]O
O
O
R2R1n
[Zn]
O
O
OP
O
R2
R1: :
[Zn] OP +OO
O
R2R1
STEP 3
Cyclic Carbonate
Polycarbonate
Accessible Site for Substrate Binding
13
repetition of this process leads to the production of polycarbonate. An impurity within
the polymer involves the consecutive ring opening of the epoxide leading to ether
linkages which greatly diminish the copolymer’s physical and thermal properties.
Another side reaction in this process involves the production of cyclic carbonate
resulting from the backbiting mechanism proposed by Kuran, in which the copolymer
weakly interacts with the metal center allowing the alkoxy oxygen to attack the
carbonyl carbon in a nucleophilic acyl substitution (Step 3).19b
Recently, Darensbourg has utilized the active (salen)CrCl catalyst23, developed
by Jacobsen and co-workers24 for the asymmetric ring opening (ARO) of epoxides
(Figure 1.4). In the copolymerization CO2 and CHO, an initial TON and TOF of 250
mol CHO consumed . mol Cr-1 and 10.4 mol CHO consumed . mol Cr-1 . hr-1 were
obtained, respectively, for a 24 hr reaction at 800 psi CO2 pressure and 80ºC. A key
difference between these chromium based catalyst and the aforementioned zinc catalyst
(e.g., zinc phenoxide) lies in the spacial location of the nucleophile relative to the
substrate binding site. Such geometrical orientation is analogous to the
tetraphenylporphinato aluminum and chromium chloride systems developed by Inoue25,
and Kruper and Dellar26, respectively, in which the square pyramidal nature of the
complex renders the nucleophile trans to the open site for substrate binding and
activation (Figure 1.5).
14
Figure 1.4. Chromium-based catalysts for the copolymerization of CO2 and epoxides.
N N
O O
Cr
Cl
N
N N
N
Cr
Cl
Jacobsen's Catalyst
Chromium Porphyrin Catalyst
15
Figure 1.5. Spacial orientation of nucleophile relative to substrate binding site.
A conceivable ring-opening step in the initiation process is difficult to envision due to
this trans orientation. Fortunately, Jacobsen and workers have discovered a second
order dependence with respect to the metal center for the ARO of epoxides, suggesting a
bimetallic intermediate (Scheme 1.3).24a,b
Scheme 1.3
In this step, the nucleophile of one chromium center effectively attacks the epoxide
bound to a second chromium center.
The use of neutral nitrogen donors as co-catalysts has been found to greatly enhance
catalytic activity. With the use of 2.25 equivalents of N-methyl imidazole, the catalyst
initially exhibited TON’s of TOF’s on the order of 404 mol CHO consumed . mol Cr-1
and 16.8 mol CHO consumed . mol Cr-1 hr-1, respectively. That is, increasing electron
density at the metal center creates a better nucleophile, and enhances the rate of
Cr Cl O
R1
R2
Cr Cl
Cr
Cl
Substrate Binding Sitetrans to Nucleophile
16
copolymer production. The main drawback of using neutral donors (i.e., Lewis bases) is
the long induction period associated with initiation, as these auxiliary ligands effectively
compete with epoxide and decrease the concentration of the epoxide bound species
(Scheme 1.3). Furthermore, studying the propagation step (polymer growth) by
monitoring the v(CO2) stretching frequency in situ, revealed a first order dependence on
metal center. Assuming a Jacobsen initiation step, propagation is presumed to take place
via nucleophilic attack of the alkoxy oxygen to a weakly interacting epoxide on one face
of the salen ligand (Scheme 1.4).
Scheme 1.4
It is the purpose of these studies presented in this dissertation to address several
issues: (1) Will the development of (salen)CrX (X = Br, OPh) catalysts bearing better
leaving groups eliminate the induction periods using N-MeIm? (2) What is the effect of
utilizing stronger donor auxiliaries such as tertiary phosphines? (3) What is the
importance of having the chromium complex adopting a square pyramidal geometry
where the initiating species is trans to the open site for epoxide binding? (4) What is the
effect on catalytic activity if the metal is varied (e.g., Fe)? The finding of these issues
should aid in the development of better catalytic salen systems.
Cr
OPO
R1
R2
L
L = Neutral DonorP = Polymer Chain
17
CHAPTER II
SYNTHESIS OF NICKEL AND PALLADIUM SALICYLALDIMINATO
1,3,5-TRIAZA-7-PHOSPHAADAMANTANE (PTA) COMPLEXES*
INTRODUCTION
Presently, most α-olefins are polymerized through the use of heterogeneous Ziegler-
Natta catalysts or metallocene catalysts in order to achieve high molecular weight
polymers.4 Both of these systems are based on early transition metals, and although
these catalysts are very active, they are highly oxophilic and vulnerable to
decomposition. Therefore, extra purification costs must be added to the industrial
polymerization process in order to assure high conversions and high molecular weight
polymers. Consequently, attention has been turned to late transition metals which are
less oxophilic and therefore able to tolerate functional-containing monomers.5 The
copolymerization of functionalized monomers with ethylene has led to new polymeric
materials with enhanced adhesive properties. In addition, catalytic activities and
polymer molecular weights obtained employing these catalysts rival those achieved by
Ziegler-Natta and metallocene catalytic systems. A drawback of these systems involves
competing β-elimination which leads to low molecular weight polymers. This is the
premise of the SHOP (Shell Higher Olefin Polymerization) process using the
_______________
* Reproduced in part with permission from Darensbourg, D. J.; Ortiz, C. G.; Yarbrough, J. C. Inorg. Chem. 2003, 42, 6915. Copyright 2003 American Chemical Society.
18
[(OCH(R1)CH(R2)PPh2)Ni(L)(R)] catalyst developed in the late 1960’s by Keim and co-
workers.27 This latter process is currently used to produce higher molecular weight
α−olefins which may be later converted to other useful products (e.g., detergents).
One of the most notable and well understood ethylene polymerization systems
utilizes Brookhart’s cationic β-diimine catalysts [(ArN=C(R)C(R’)=NAr)M(L)(CH3)]+
(M = Ni, Pd).5,28 Optimization of the catalyst’s activity over the years by ligand
modification has led to the industrial implementation of the catalyst for the
polymerization of ethylene.29 Of primary interest to this study is the catalyst developed
by Grubbs and co-workers which is based on the salicylaldimine ligand framework
(Figure 2.1).9 Similar to the SHOP catalyst, the ligand is mono-anionic, rendering a
neutral catalyst which is devoid of bulky counterions. However, unlike the SHOP
catalyst, the incorporation of sterically demanding groups on the ligand effectively
shields the axial sites of the metal center thereby allowing enchainment to predominate
over β-hydride elimination processes. As with most olefin polymerization catalysts, a
co-catalyst is usually needed to initiate polymerization. In the case of metallocene4d or
Brookhart’s28 catalysts, an excess of an aluminum co-catalyst such as methyl
aluminoxane (MAO) must be used. For 1, a phosphine scavenger such as Ni(COD)2
(COD = 1,5-cyclooctadiene) is needed to remove the phosphine from the metal center
and allow alkene coordination.9 An obvious drawback to this latter process is that this
co-catalyst is highly air-sensitive and prone to autocatalytic decomposition.
19
R3
i-Pr
O
N
Ni
PPh3
Ph
i-Pr
1a-f
R1R2
R4
a. R3 = NO2, R1 = R2 = R4 = Hb. R1 = OMe, R2 = R3 = R4 = Hc. R3 = CH(CH)2CH = R4, R1 = R2 = Hd. R1 = R3 = Cl, R2 = R4 = He. R1 = C6H5, R2 = R3 = R4 = Hf. R1 = 9-anthra, R2 = R3 = R4 = H
Figure 2.1. Salicylaldiminato nickel(II) catalyst.
The purpose of this study is to explore the effect of incorporating a water-soluble
phosphine (WSP) into 1 and using a biphasic toluene/water solvent mixture to allow
irreversible phosphine dissociation, thereby eliminating the need for a phosphine
scavenger. Although it has been shown in Grubbs’ system that initiation can take place
without the need of a co-catalyst by using a more sterically demanding group in the R1
position of the ligand, many of the active derivatives require co-catalysts.9a The
polymerization of various olefins has been achieved in water; however, to our
knowledge, this is the first attempt to use a biphasic solvent system to generate the active
20
catalyst in the organic phase while allowing the WSP to enter and remain in the aqueous
phase.3
The use of WSP in catalysis was first commercialized by Ruhrchemie in 1984 for
the hydroformylation of higher molecular weight α-olefins to predominantly form
terminal aldehydes.30 The system uses the tri-sulfonated triphenylphosphine ligand,
meta-TPPTS (Figure 2.2),31 coordinated to rhodium to form the active
RhH(CO)(TPPTS)3 catalyst. Another WSP, which is of main interest to this study, is the
heterocyclic, aliphatic 1,3,5-triaza-7-phosphaadamantane (PTA)11, and its acylated
derivative, 3,7-Diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA)11d. Many
complexes incorporating this ligand have been prepared, and the ruthenium and rhodium
derivatives have been found to be effective catalysts in the hydrogenation of various
unsaturated hydrocarbons.12a-c, 32 Herein, we wish to report the synthesis of various PTA
derivatives of 1 by two routes, (a) ligand exchange reaction and (b) direct synthesis, as
well as the solid state characterization of many of these derivatives.
21
Figure 2.2. Examples of WSP used in aqueous catalysis.
N NN
P
N NN
P
O
O
P
SO3- M+SO3
- M+
SO3- M+
PTA DAPTA
meta-TPPTS
P
para-TPPTS
SO3- M+
SO3- M+
+M -O3S
22
EXPERIMENTAL
Materials and Methods
Unless otherwise indicated, all reactions were carried out under an inert argon
atmosphere using standard Schlenk and drybox techniques. Prior to their use, all
solvents were distilled using standard techniques. 2-hydroxy-3-phenylbenzaldehyde was
prepared from the corresponding phenol33, and all other benzaldehydes were purchased
from Aldrich Chemicals. Ligands a-g were prepared by the condensation reaction of the
corresponding aldehyde with commercially available 2,6-diisopropyl aniline. PTA11b,
DAPTA11d, (TMEDA)Ni(CH3)234a, (TMEDA)Pd(CH3)2
34b, and 1a9a were prepared
according to literature procedures.
1H, 13C, and 31P NMR data were obtained using a Varian Unity+ 300 MHz NMR
instrument. 1H and 13C chemical shifts were referenced according to the deuterated
solvent used. The 31P chemical shifts were referenced using an external 85% H3PO4
sample. Elemental Analysis was conducted by Canadian Microanalytical Inc.
Preparation of Nickel Salicylaldiminato PTA Complexes by Ligand Exchange with
1 (2a)
To a 50 mL Schlenk flask containing 1a (100 mg, 0.138 mmol) in 3 mL of toluene
was added a concentrated methanol solution of PTA (23.7 mg, 0.152 mmol, in 5 mL of
MeOH). A yellow precipitate immediately formed, and the reaction was stirred
overnight. After filtration and washing with pentane, the solid was re-dissolved in
CH2Cl2 and filtered. After removal of the solvent under vacuum, 2a was obtained.
23
2a (R3=NO2, R1=R2=R4=H): 1H NMR (300 MHz, CD2Cl2, δ): 1.00 (d, 3JHH=6.60
Hz, 6H, CH(CH3)2), 1.29 (d, 3JHH=6.90 Hz, 6H, CH(CH3)2), 3.52 (sept, 3JHH=6.90 Hz,
2H, CH(CH3)2), 3.91 (s, 6 H, NCH2N), 4.313 (dd, 2JHP=19.79 Hz, 2JHH=12.90 Hz, 6H,
PCH2N), 6.50-6.59 (m, 3H, Ar), 6.79-6.85 (m, 3H, Ar), 6.89-6.94 (m, 3H, Ar), 7.17-7.25
(m, 1H, Ar), 8.00 (d, 4JHP=8.10 Hz, 1H, HC=N), 8.11-8.17 (m, 2H, Ar). 13C NMR (75
MHz, CD2Cl2, δ): 22.23, 25.61, 28.74, 50.46 (d, 1JCP=14.86 Hz, P-C-N), 73.20 (d,
3JCP=6.26 Hz, N-C-N), 118.03, 122.68, 122.74, 126.10, 126.19, 128.67, 132.33, 136.02,
137.18, 137.23, 139.97, 142.49, 143.23, 148.73, 165.82, 171.03. 31P NMR (121 MHz,
CD2Cl2, δ): -57.76. Yield: 58.3%. Elem. Anal. Calcd. for C31H38N5O3PNi: C, 60.22%;
H, 6.19%; N, 11.33%; Exp.: C, 61.32%; H, 6.07%; N, 10.70%.
Direct Synthetic Approach for the Preparation of Nickel and Palladium
Salicylaldiminato PTA Complexes (3a-f and 4a-f)
To a 50 mL Schlenk flask containing (TMEDA)Ni(CH3)2 (200 mg, 0.976 mmol) in
10mL of toluene at –300C, PTA (170 mg, 1.07 mmol) in 5mL of methanol was
introduced via cannula. To this mixture, Ha (318 mg, 0.976 mmol) in 10mL of toluene
at –30ºC was slowly cannulated into the flask, and the solution was stirred for 30
minutes. Subsequently, the temperature was raised to room temperature, and the light
red solution was further stirred overnight. After stirring overnight, the solvent was
removed in vacuo until approximately 5mL remained, and 20mL of cold (-780C) pentane
was added, resulting in the formation of a yellow precipitate. The solid was collected by
cold cannula filtration and washed (3 x 5mL) with cold (-780C) pentane, affording 3a in
60% yield (350 mg). The other salicylaldiminato nickel and palladium
24
((TMEDA)Pd(CH3)2 was used as the palladium source) PTA complexes were prepared
in an analogous fashion. Complexes 3a-e and 4a-e were all obtained as yellow solids in
good yields.
3a (R3=NO2, R1=R2=R4=H): 1H NMR (300 MHz, C6D6, δ): -1.33 (s, 3H, Ni-CH3),
0.98 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2), 1.35 (d, 3JHH=6.90 Hz, 6H, CH(CH3)2), 3.58
(sept, 3JHH=6.90 Hz, 2H, CH(CH3)2), 3.73 (s, 6H, NCH2N), 4.09 (dd, 2JHP=32.69 Hz,
2JHH=12.90 Hz, 6H, PCH2N), 6.41 (t, 3JHH=9.60 Hz, 1H, Ar), 7.05-7.13 (m, 3H, Ar), 7.46
(s, 1H, HN=C), 7.98 (d, 3JHH=2.94, 1H, Ar), 8.11 (dd, 3JHH=2.94 Hz, 3JHH=9.60 Hz, 1H,
Ar). 13C NMR (75 MHz, C6D6, δ): –15.84 (d, 2JCP=4.25 Hz, Ni-CH3), 23.47, 25.09,
29.00, 50.85 (d, 1JCP=5.93 Hz, P-C-N), 73.93 (d, 3JCP=4.85 Hz, N-C-N), 122.93, 124.14,
127.36, 129.18, 132.84, 141.01, 165.92. 31P NMR (121 MHz, C6D6, δ): -47.10.
3b (R1=OMe, R2=R3=R4=H): 1H NMR (300 MHz, C6D6, δ): -1.26 (s, 3H, Ni-CH3),
1.04 (d, 3JHH=6.30 Hz, 6H, CH(CH3)2), 1.40 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2), 3.42 (s,
3H, OCH3), 3.82 (sept, 3JHH=6.60 Hz, 2H, CH(CH3)2), 4.00 (s, 6H, NCH2N), 4.08 (dd,
2JHP=22.79 Hz, 2JHH=13.20 Hz, 6H, PCH2N), 6.46 (t, 3JHH=7.80 Hz, 1H, Ar), 6.59 (d,
3JHH=7.50 Hz, 1H, Ar), 6.67 (d, 3JHH=7.20 Hz, 1H, Ar), 6.94-7.48 (m, 3H, Ar), 7.90 (s,
1H, HC=N). 13C NMR (75 MHz, C6D6, δ): –19.71 (d, 2JCP=4.36 Hz, Ni-CH3), 21.10,
22.82, 26.50, 48.38 (d, 1JCP=6.03 Hz, P-C-N), 53.46 (d, 3JCP=4.90 Hz, N-C-N), 71.29
(OCH3), 111.10, 116.88, 121.58, 123.80, 124.48, 128.34, 132.51, 139.29, 147.16,
151.42, 156.86, 163.32. 31P NMR (121 MHz, C6D6, δ): -54.56. Yield 51.1%. Elem.
Anal. Calcd. for C27H39N4OPNi: C, 59.91%; H, 7.26%; N, 10.35%; Exp.: C, 59.86%; H,
7.10%; N, 10.55%.
25
3c (R3=CH(CH)2CH=R4, R1=R2=H): 1H NMR (300 MHz, C6D6, δ): -1.26 (s, 3H,
Ni-CH3), 1.06 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2), 1.39 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2),
3.83 (s, 6H, NCH2N), 3.90 (sept, 3JHH=6.90 Hz, 2H, CH(CH3)2), 4.02 (dd, 2JHP=34.19
Hz, 2JHH=13.20 Hz, 6H, PCH2N), 6.96-7.14 (m, 6H, Ar), 7.46-7.52 (m, 3H, Ar), 8.87 (s,
1H, HC=N). 13C NMR (75 MHz, C6D6, δ): -18.68 (d, 2JCP=4.30 Hz, Ni-CH3), 21.14,
23.03, 26.51, 48.33 (P-C-N), 71.39 (N-C-N), 107.33, 116.44, 120.09, 121.67, 123.70,
124.52, 125.05, 127.41, 132.99, 133.52, 139.67, 148.00, 157.31, 165.72. 31P NMR (121
MHz, C6D6, δ): -60.88. Yield: 55.0%. Elem. Anal. Calcd. for C30H39N4OPNi: C,
62.41%; H, 6.81%; N, 9.70%; Exp.: C, 62.83%; H, 6.74%; N, 10.48%.
3d (R1=R3=Cl, R2=R4=H): 1H NMR (300 MHz, C6D6, δ): -1.29 (s, 3H, Ni-CH3),
0.99 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2), 1.38 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2), 3.66
(sept, 3JHH=6.60 Hz, 2H, CH(CH3)2), 3.93 (s, 6H, NCH2N), 4.04 (dd, 2JHP=22.79 Hz,
2JHH=13.20 Hz, 6H, PCH2N), 6.71 (d, 3JHH=2.70 Hz, 1H, Ar), 7.07-7.13 (m, 3H, Ar),
7.38 (d, 3JHH=2.70 Hz, 1H, Ar), 7.54 (s, 1H, HC=N). 13C NMR (75 MHz, C6D6, δ): -
18.65 (d, 2JCP=3.62 Hz, Ni-CH3), 21.06, 22.77, 26.56, 48.61 (d, 1JCP=8.90 Hz, P-C-N),
71.40 (d, 3JCP=5.50 Hz, N-C-N), 115.47, 117.90, 121.69, 124.87, 126.47, 129.58,
131.53, 138.81, 146.38, 158.35, 162.81. 31P NMR (121 MHz, C6D6, δ): -59.36. Yield:
72.4%.
3e (R1=C6H5, R2=R3=R4=H): 1H NMR (300 MHz, C6D6, δ): -1.27 (s, 3H, Ni-CH3),
1.04 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2), 1.37 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2), 3.66 (s,
6H, NCH2N), 3.82 (t, 3JHH=6.90 Hz, 2H, CH(CH3)2), 3.91 (dd, 2JHP=42.29 Hz,
2JHH=13.20 Hz, 6 H, PCH2N), 6.54 (t, 3JHH=7.50 Hz, 1H, Ar), 6.94 (d, 3JHH=7.80 Hz, 1H,
26
Ar), 7.07-7.22 (m, 6H, Ar), 7.29 (d, 3JHH=6.90 Hz, 1H, Ar), 7.48 (d, 3JHH=6.90 Hz, 2H,
Ar), 7.90 (s, 1H, HC=N). 13C NMR (75 MHz, C6D6, δ): –19.43 (d, 2JCP=4.22 Hz, Ni-
CH3), 21.08, 22.87, 26.51, 48.08 (d, 1JCP=12.22 Hz, P-C-N), 71.12 (d, 3JCP=4.60 Hz, N-
C-N), 112.14, 117.81, 121.63, 124.64, 126.21, 128.35, 132.51, 133.10, 133.67, 139.31,
139.86, 147.01, 162.98, 163.90. 31P NMR (121 MHz, C6D6, δ): -55.34. Yield: 69.7%.
Elem. Anal. Calcd. for C32H41N4OPNi: C, 65.47%; H, 6.98%; N, 9.55%; Exp.: C,
65.49%; H, 6.95%; N, 9.42%.
4a (R3=NO2, R1=R2=R4=H): 1H NMR (300 MHz, C6D6, δ): –0.19 (d, 3JHP=3.28 Hz,
3H, Pd-CH3), 1.00 (d, 3JHH=6.90 Hz, 6H, CH(CH3)2), 1.32 (d, 3JHH=6.90 Hz, 6H,
CH(CH3)2), 3.29 (sept, 3JHH=6.90 Hz, 2H, CH(CH3)2), 3.83 (s, 6H, NCH2N), 3.99 (dd,
2JHP=30.59 Hz, 2JHH=13.50 Hz, 6H, PCH2N), 6.65 (d, 3JHH=9.60 Hz, 1H, Ar), 7.14 (d,
3JHH=3.00 Hz, 1H, Ar), 7.21-7.17 (m, 2H, Ar), 7.53 (d, 4JHP=10.20 Hz, 1H, HC=N), 8.11
(d, 3JHH=2.70 Hz, 1H, Ar), 8.22 (dd, 3JHH=3.00 Hz, 3JHH=9.60 Hz, 1H, Ar). 13C NMR (75
MHz, C6D6, δ): –7.88 (d, 2JCP=17.73 Hz, Pd-CH3), 23.32, 25.00, 28.73, 50.95 (d,
1JCP=16.74 Hz, P-C-N), 73.60 (d, 3JCP=6.11 Hz, N-C-N), 118.54, 123.90, 127.44, 130.15,
135.21, 136.30, 141.02, 147.35, 166.63, 173.39. 31P NMR (121 MHz, C6D6, δ): -46.18.
Yield: 95.7%. Elem. Anal. Calcd. for C26H36N5O3PPd: C, 51.71%; H, 5.96%; N,
11.60%; Exp.: C, 52.16%; H, 6.30%; N, 11.63%.
4b (R1=OCH3, R2=R3=R4=H): 1H NMR (300 MHz, C6D6, δ): –0.18 (d, 3JHP=3.60
Hz , 3H, Pd-CH3), 1.01 (d, 3JHH=6.90 Hz, 6H, CH(CH3)2), 1.32 (d, 3JHH=6.60 Hz, 6H,
CH(CH3)2), 3.47 (sept, 3JHH=6.90 Hz, 2H, CH(CH3)2), 3.54 (s, 3H, OCH3), 3.98-4.08
(m, 12H, PCH2N, NCH2N), 6.43 (t, 3JHH=7.21 Hz, 1H, Ar), 6.71 (m, 2H, Ar), 7.92 (d,
27
4JHH=11.43 Hz, 1H, HC=N). 13C NMR (75 MHz, C6D6, δ): –9.33 (d, 2JCP=13.80 Hz, Pd-
CH3), 23.36, 25.14, 28.62 51.28 (d, 1JCP=15.24 Hz, P-C-N), 56.46 (OCH3), 73.83 (d,
3JCP=7.62 Hz, N-C-N), 112.57, 115.46, 119.49, 123.94, 126.93, 128.61, 141.70, 148.46,
154.17, 161.82, 166.45. 31P NMR (121 MHz, C6D6, δ): -44.74. Yield: 91.2%. Elem.
Anal. Calcd. for C27H39N4O2PPd: C, 54.97%; H, 6.61%; N, 9.50%; Exp.: C, 55.21%; H,
6.50%; N, 9.41%.
4c (R3=CH(CH)2CH=R4, R1=R2=H): 1H NMR (300 MHz, C6D6, δ): –0.20 (d,
3JHP=3.90 Hz, 3H, Pd-CH3), 1.02 (d, 3JHH=6.90 Hz, 6H, CH(CH3)2), 1.30 (d, 3JHH=6.90
Hz, 6Hz, CH(CH3)2), 3.54 (sept, 3JHH=7.20 Hz, 2H, CH(CH3)2), 3.85 (s, 6H, N-C-N),
3.93 (dd, 2JHP= 29.39 Hz, 2JHH=13.20 Hz, 6H, PCH2N), 6.95-7.13 (m, 5H, Ar), 7.45(d,
3JHH=8.10 Hz, 1H, Ar), 7.52 (d, 3JHH=9.30 Hz, 1H, Ar), 7.57 (d, 3JHH=8.70 Hz, 1H, Ar),
8.95 (d, 4JHP=11.95 Hz, 1H, HC=N). 13C NMR (75 MHz, C6D6, δ): –8.88 (d, 2JCP=15.31
Hz, Pd-CH3), 23.45, 25.37, 28.63, 51.05 (d, 1JCP=15.31 Hz, P-C-N), 73.74 (d, 3JCP=7.62
Hz, N-C-N), 119.23, 122.10, 124.04, 126.95, 127.38, 127.46, 128.92, 129.69, 129.89,
136.38, 137.29, 142.13, 149.39, 160.09. 31P NMR (121 MHz, C6D6, δ): -47.18. Yield:
98.5%. Elem. Anal. Calcd. for C30H39N4OPPd: C, 59.20%; H, 6.41%; N, 9.21%; Exp.:
C, 60.01%; H, 6.48%; N, 8.81%.
4d (R1=R3=Cl, R2=R4=H): 1H NMR (300 MHz, C6D6, δ): –0.19 (d, 3JHP=3.30 Hz,
3H, Pd-CH3), 1.00 (d, 3JHH=6.90 Hz, 6H, CH(CH3)2), 1.34 (d, 3JHH=6.90 Hz, 6H,
CH(CH3)2), 3.34 (sept, 3JHH=6.60 Hz, 2H, CH(CH3)2), 3.98 (s, 6H, NCH2N), 3.99 (d,
2JHP=20.39 Hz, 2JHH=12.90 Hz, 6H, PCH2N), 6.77 (d, 3JHH=2.70 Hz, 1H, Ar), 7.13-7.18
(m, 3H, Ar), 7.51 (d, 3JHH=3.00 Hz, 1H, Ar), 7.57 (d, 4JHP=10.50 Hz, 1H, HC=N). 13C
28
NMR (75 MHz, C6D6, δ): –8.40 (d, 2JCP=13.73 Hz, Pd-CH3), 23.33, 25.07, 28.67, 51.24
(d, 1JCP=16.82 Hz, P-C-N), 73.66 (d, 3JCP=7.62 Hz, N-C-N), 116.66, 120.34, 124.04,
127.32, 129.40, 133.93, 134.72, 141.16, 147.69, 162.56, 166.02. 31P NMR (121 MHz,
C6D6, δ): -44.54. Yield: 82.8%. Elem. Anal. Calcd. for C26H35N4OPCl2Pd: C, 49.69%;
H, 5.57; N, 8.92%; Exp.: C, 50.49%; H, 5.59%; N, 8.92%.
4e (R1=C6H5, R2=R3=R4=H): 1H NMR (300 MHz, C6D6, δ): -0.17 (d, 3JHP=3.60 Hz,
3H, Pd-CH3), 1.02 (d, 3JHH=6.90 Hz, 6H, CH(CH3)2), 1.31 (d, 3JHH=6.90 Hz, 6H,
CH(CH3)2), 3.47 (sept, 3JHH=7.20 Hz, 2H, CH(CH3)2), 3.70 (s, 6H, NCH2N), 3.91 (dd,
2JHP=20.09 Hz, 2JHH=13.50 Hz, 6H, PCH2N), 6.54 (t, 3JHH=6.90 Hz, 1H, Ar), 6.93 (m,
1H, Ar), 7.12 (m, 1H, Ar), 7.24 (t, 3JHH=7.20 Hz, 2H, Ar), 7.40 (m, 1H, Ar), 7.59-7.62
(m, 2H, Ar), 7.93 (d, 4JHP=11.70 Hz, 1H, HC=N). 13C NMR (75 MHz, C6D6, δ): -7.88
(d, 2JCP=54.59 Hz, Pd-CH3), 23.98, 25.82, 29.22, 51.50 (d, 1JCP=15.23 Hz, P-C-N),
73.70(d, 3JCP=7.62 Hz, N-C-N), 113.53, 120.07, 123.61, 126.42, 126.64, 130.45, 135.83,
136.56, 141.17, 142.02, 147.67, 166.53, 166.34. 31P NMR (121 MHz, C6D6, δ): -46.16.
Yield: 67.6%.
Preparation of Palladium Salicylaldiminato DAPTA Complex (4d-DAPTA)
The complex was prepared in the same manner as all other PTA complexes. As with
the PTA complexes, this derivative is yellow in color and obtained in excellent yield.
4d-DAPTA (R1=R3=Cl; R2=R4=H): 1H NMR (300 MHz, C6D6, δ): -0.14 (d,
3JHP=3.60 Hz, 3H, Pd-CH3), 0.97 (dd, 3JHH=6.60 Hz, 3JHH=2.70 Hz, 6H, CH(CH3)2), 1.29
(dd, 3JHH=6.60 Hz, 3JHH=6.00 Hz, 6H, -C(O)CH3), 1.80 (d, 3JHH=6.60 Hz, 6H,
CH(CH3)2), 2.97 – 3.02 (m, 1H, DAPTA), 3.24 – 3.34 (m, 5H, DAPTA), 3.51 (d,
29
3JHH=14.10, 1H, DAPTA), 3.62 – 3.67 (m, 1H, DAPTA), 4.21 (d, 3JHH=13.80 Hz, 1H,
DAPTA), 4.23 – 4.51 (m, 1H, DAPTA), 6.75 (d, 3JHH=2.7 Hz, 1H, Ar), 7.11 – 7.15 (m,
2H, Ar), 7.48 (d, 3JHH=2.7 Hz, 1H, Ar), 7.55 (d, 4JHP=11.40 Hz, 1H, HC=N). 13C NMR
(75 MHz, C6H6, δ): -7.65 (d, 2JCP=12.15 Hz, Pd-CH3), 21.09, 22.78, 24.56, 28.23, 37.28
(d, 1JCP=22.05 Hz, P-C-N), 41.97 (d, 1JCP=19.73 Hz, P-C-N), 47.13 (d, 1JCP=24.30 Hz, P-
C-N), 61.50 (d, 4JCP=4.50 Hz, C(O)CH3), 66.61 (d, 4JCP=4.50 Hz, C(O)CH3), 116.63,
119.75, 123.60, 123.68, 125.53, 127.06, 128.40, 128.74, 129.17, 133.49, 134.44, 140.69
(d, 3JCP=9.15 Hz, C=N), 146.91, 168.46 (C=O), 169.23(C=O). 31P NMR (121 MHz,
C6D6, δ): -24.12. IR (CH2Cl2): v(C=O)=1605 cm-1. Yield: 96.8%. Elem. Anal. Calcd.
for C29H39N4O3PCl2Pd: C, 49.79%; H, 5.57; N, 8.01%; Exp.: C, 51.96%; H, 5.81%; N,
7.66%.
Polymerization of Ethylene Using 2a
To a 100 mL glass miniclave reactor was added approximately 10 mL of degassed
water, followed by the addition of 2a (100 mg, 0.162 mmol) in 10 mL of toluene.
Ethylene was added until the total pressure was 8 atm. The mixture was stirred for
approximately 5 hr at ambient temperature. Subsequent to venting the system, the
toluene layer was separated and toluene was removed by roto-evaporation leaving
behind no polyethylene.
30
RESULTS AND DISCUSSION
The preparation of 1 was achieved by using the trans-(PPh3)2NiCl(Ph) precursor
and one equivalent of the Na+a-f salts as previously described.9 An advantage to using
trans-(PPh3)2NiCl(Ph) is its air-stable nature, as perfect, large, maroon crystals are
formed in air. Surprisingly, the solid-state structure of the complex has never been
published, and herein, we wish to highlight some of its physical data. Crystal data, and
selected bond distances and angles are tabulated in Table 2.1 and Table 2.2, respectively.
A thermal ellipsoid representation of the complex is provided in Figure 2.3 showing
50% probability. Typical of Ni(II) complexes, the metal center adopts a slightly
distorted square planar geometry in which the two phosphines lie trans to one another.
The P(1)-Ni(1)-P(2) and C(1)-Ni(1)-Cl(1) bond angles were found to be 175.33(3) and
169.76(6)˚, respectively. The phenyl ring is also positioned in a manner to decrease
electronic repulsions, as the C6H5 plane is perpendicular to that formed by the complex.
The Ni(1)-C(1), Ni(1)-Cl(1), Ni(1)-P(1), and Ni(1)-P(2) bond distances were found to be
1.887(2), 2.2327(6), 2.2114(6), and 2.2155(6) Å, respectively.
Table 2.1. Crystallographic data for complex, trans-(PPh3)2NiCl(Ph). crystal system triclinic V, Å3 1727.4(4) space group P/1 Z 2 a, Å 11.0038(13) T, K 110 b, Å 11.8570(14) d(calcd), g/cm3 1.397 c, Å 13.9008(16) Abs, coeff, mm-1 0.808 α, deg 96.462(2) R,a %[I>2σ(I)] 3.44 β, deg 94.075(2) Rw
a %[I>2σ(I)] 5.97 γ, deg 105.442(2)
31
Table 2.2. Selected bond distances (Ǻ) and angles for complex trans-(PPh3)2NiCl(Ph). Ni(1)-C(1) 1.887(2) Ni(1)-P(1) 2.2114(6) Ni(1)-Cl(1) 2.2327(6) Ni(1)-P(2) 2.2155(6) C(1)-Ni(1)-Cl(1) 169.76(6) P(1)-Ni(1)-Cl(1) 90.05(2) P(1)-Ni(1)-P(2) 175.33(3) P(2)-Ni(1)-Cl(1) 94.13(2) C(1)-Ni(1)-P(1) 89.20(6) C(1)-Ni(1)-P(2) 87.04(6) Initially, we attempted the synthesis of the PTA derivatives of nickel
salicylaldiminato complexes using the commonly employed protocol of rapidly stirring a
biphasic mixture consisting of the PPh3 analog complex (e.g., 1a) in toluene with excess
PTA in water at ambient temperature. However, under these reaction conditions no
ligand substitution occurred. This procedure is generally successful since PTA has
smaller steric requirements and is a more donating ligand than PPh3.35, 36 Evidently, in
this instance there is little PTA in the organic phase and vice versa. This conclusion is
supported upon carrying out the reaction in a homogeneous toluene/methanol mixture in
which 1a and PTA were first dissolved in toluene and methanol, respectively (Scheme
2.1). That is, upon addition of the concentrated PTA solution to a solution of 1a in
toluene, a yellow precipitate formed immediately. The identity of this yellow derivative
(2a) was confirmed to be the PTA analog of 1a by NMR spectroscopy, elemental
analysis, and X-ray crystallography.
32
Figure 2.3. Thermal ellipsoid representation of trans-(PPh3)2NiCl(Ph) showing 50% probability.
33
Scheme 2.1
R3
i-Pr
O
N
Ni
PPh3
Ph
i-Pr
+ N NN
P
Toluene/ MeOHr.t., overnight-PPh3
R3
i-Pr
O
N
Ni
Ph
i-Pr
N
N
N
P
1a-e
PTA
R1R2
R4
R1R2
R4
2a-e
The 1H NMR spectrum of 2a in CD2Cl2 displayed many characteristic resonances.
Importantly, the signals corresponding to the terminal isopropyl groups (CH(CH3)2)
were split into two sets of doublets indicating a rotation barrier of the aniline moiety
upon ligand coordination, consistent with what is observed for other salicylaldiminato
complexes.37, 38 Hydrogen resonances due to the PTA ligand are located between 3.7-4.2
ppm, with the NCH2N hydrogens appearing as singlets. The resonance due to the
PCH2N hydrogen is observed as a doublet of doublets as a result of coupling to
phosphorus and the geminal proton (2JHP~25 Hz and 2JHH~13 Hz). The aldimine
(HC=N) hydrogen is displayed as a doublet near 8.0 ppm with phosphorus coupling on
the order of 8.1 Hz, as previously reported for the PPh3 derivatives (e.g., 1).9 The 31P
NMR resonance in 2a (-57.76 ppm) is shifted in CD2Cl2 40.5 ppm downfield from free
PTA at -98.3 ppm in water.
Alternatively, salicylaldiminato PTA complexes may be prepared via a direct
synthetic approach in which (TMEDA)M(CH3)2 (M = Ni, Pd) is used as the metal
34
precursor.34 Liberating methane in the process, the metal precursor is reacted with PTA
and the corresponding salicylaldimine at -30ºC to yield the nickel and palladium
complexes (3 and 4) in moderate to quantitative yields (Scheme 2.2). The 1H NMR
resonance of the aldimine hydrogen in 4 displays phosphorus coupling (JHP ~ 11 Hz)
with chemical shift values similar to those observed for 1.9 Resonances due to the M-
CH3 protons are consistent with other group 10 complexes, occurring in the 0 to -1 ppm
range.38, 39 Interestingly, the nickel derivatives, 3, do not exhibit 31P coupling of the
methyl and aldimine hydrogen atoms to PTA. This is in contrast to the SHOP catalyst
developed by Keim and co-workers where 31P coupling to the methyl hydrogens was
observed (JHP ~7.4 Hz).39a Complex 4, however, does exhibit 31P coupling (JHP ~ 5 Hz)
of the Pd-CH3 hydrogen atoms to PTA. A representative 1H NMR spectrum of 4d is
presented in Figure 2.4.
Scheme 2.2
N NN
P
N
N
M
i-Pr
i-PrN
HO
R1 R2
R3
R4R3
i-Pr
O
N
M
CH3
i-Pr
N
NN
P
R1R2
R4
+ +
M = Ni (3a-f) Pd (4a-f)
Toluene/MeOH1. -30ºC, 30 min2. r.t., overnight-CH4, TMEDA
M = Ni Pd
a-f
PTA
35
Figure 2.4. Representative 1H NMR spectrum of Pd(1/2Sal-Cl)PTA, 4d.
1.5 1.0 0.5 0.0
7.55
7.58
Pd-CH3
CH(CH3)
CH(CH3) HN=C, JHP=10.5 Hz
7.59 7.58 7.57 7.56 7.55 7.54 7.53 7.52
JHP = 3.3 Hz
1.5 1.0 0.5 0.0
7.55
7.58
Pd-CH3
CH(CH3)
CH(CH3) HN=C, JHP=10.5 Hz
7.59 7.58 7.57 7.56 7.55 7.54 7.53 7.52
JHP = 3.3 Hz
36
The 13C NMR spectra of complexes 3 and 4 also display unique resonances. The
Ni-CH3 carbon resonances are observed in the -15 to -20 ppm range with 31P coupling on
the order of 4 Hz. In contrast, the Pd-CH3 carbon resonances are displayed further
downfield (-7 to -9 ppm) with a larger 31P coupling (JCP~ 15 Hz). The NCH2N and
PCH2N carbons of the PTA ligand are observed in the 50 and 70 ppm region,
respectively. 31P coupling is also observed for the PCH2N carbons with approximate
values of 8 and 15 Hz for 3 and 4, respectively. As expected, a smaller 31P coupling
constant is associated with the NCH2N carbon, with JCP values on the order of 5 to 7 Hz
for 3 and 4, respectively. The 31P NMR resonances for these complexes are observed at
approximately -60 ppm and -45 ppm for 3 and 4, respectively.
The solid-state structure of the nickel(II) salicylaldimato derivative containing
the PPh3 ligand (complex 1e in Figure 2.1) has been reported by Grubbs and
coworkers.9a Herein, we describe the solid-state structure of an analogous complex, 1a,
for comparative purposes. Crystals of 1a suitable for X-ray analysis were obtained from
a solution of 1a in toluene maintained at -20ºC for approximately two weeks. Tables 2.3
and 2.4 contain the crystallographic data, and selected bond distances and angles,
respectively; whereas a thermal ellipsoid representation of complex 1a may be found in
Figure 2.5. As expected for four-coordinate d8 metal complexes, the structure of 1a
adopts a nearly ideal square planar geometry with N–Ni–P and C–Ni–O bond angles of
176.61(7) and 171.64(10)º, respectively. The isopropyl groups on the 2,6-
diisopropylbenzimine lie perpendicular to the plane created by the N, P, O, C atoms.
37
Table 2.3. Crystallographic data for complexes 1a, 2a, 4a, 4b, 3b', 3b, 3d, 4c, 4d, and 4d-DAPTA. 1a 2a 4a 4b 3b'
Cryst syst triclinic monoclinic triclinic orthorhombic monoclinic
space group P-1 P2(1)/n P-1 Pbca P2(1)/n
V, Å3 1780.6(4) 3169.3(5) 1336.4(18) 5384(4) 3947.3(8)
Z 2 4 2 8 4
a, Å 9.5718(12) 10.1182(9) 9.127(7) 12.249(6) 8.9737(11)
b, Å 12.0581(16) 20.5266(18) 10.888(8) 18.457(8) 20.255(3)
c, Å 15.784(2) 15.5267(13) 15.293(14) 23.812(11) 21.720(3)
α, deg 90.158(2) — 69.195(14) — —
β, deg 99.214(3) 100.643(2) 76.151(19) — 90.919(3)
γ, deg 97.906(3) — 71.950(12) — —
T, K 110 110 110 110 110
d(calc), g/cm3 1.349 1.474 1.501 1.453 1.286
Abs coeff, mm-1 0.633 0.874 0.791 0.780 0.669 R,a % [I > 2σ (I)] 4.79 8.10 8.00 3.43 6.11
Rw,a % 8.79 19.85 9.41 5.23 14.62
38
Table 2.3 (Continued). 3b 3d 4c 4d 4d-DAPTA
Cryst syst monoclinic monoclinic triclinic monoclinic triclinic
space group P2(1)/n P2(1)/n P-1 P2(1)/n P-1
V, Å3 2846.9(19) 2742.9(5) 1380.9(3) 2752(2) 3350.3(16)
Z 4 4 2 4 4
a, Å 11.366(4) 12.1482(15) 9.8304(11) 10.703(4) 12.530(4)
b, Å 23.445(9) 15.4883(19) 12.8719(13) 12.059(5) 15.620(4)
c, Å 11.875(5) 15.3461(14) 13.2710(14) 21.326(11) 17.576(5)
α, deg — — 115.773(2) — 77.533(5)
β, deg 115.888(7) 108.203(11) 102.892(2) 91.03(3) 85.937(5)
γ, deg — — 102.128(2) — 88.832(5)
T, K 110 110 110 110 110
d(calc), g/cm3 1.374 1.405 1.465 1.515 1.570
Abs coeff, mm-1 0.864 0.987 0.761 0.953 0.960 R,a % [I > 2σ (I)] 7.21 5.73 3.12 5.69 7.93
Rw,a % 23.43 10.72 3.85 11.45 10.24 a R = Σ || Fo | – | Fc || / ΣFo and RwF = {[Σw(Fo – Fc)2] / ΣwFo
2}½
39
Table 2.4. Selected bond distances (Å) and angles of complexes 1a, 2a, 4a, 4b, 3b', 3b, 3d, 4c, 4d and 4d-DAPTA.a
1a 2a 4a 4b 3b'
Bond Distance
M(1)-C(1) 1.893(3) 1.893(6) 2.024(9) 2.036(4) ----------
M(1)-P(1) 2.1754(8) 2.1345(18) 2.199(3) 2.1995(12) ----------
M(1)-O(1) 1.9141(19) 1.888(4) 2.094(5) 2.068(2) 1.827(3)
M(1)-N(1) 1.947(2) 1.964(5) 2.097(6) 2.087(3) 1.907(3)
Bond Angle
C(1)-M(1)-O(1) 171.64(10) 169.7(2) 176.1(3) 177.13(13) ----------
P(1)-M(1)-C(1) 84.86(8) 83.85(18) 87.7(3) 86.26(11) ----------
O(1)-M(1)-N(1) 92.86(4) 87.68(13) 88.6(2) 89.67(11) 93.37(12)
P(1)-M(1)-O(1) 89.65(6) 92.99(18) 90.44(17) 90.98(8) ----------
P(1)-M(1)-N(1) 176.61(7) 173.33(15) 175.82(19) 173.27(8) ----------
N(1)-M(1)-N(2) -------- -------- -------- -------- 178.04(12)
40
Table 2.4 (Continued).
3b 3d 4c 4d 4d-DAPTA
Bond Distance
M(1)-C(1) 1.926(8) 1.923(4) 2.026(3) 2.045(12) 2.029(8)
M(1)-P(1) 2.119(2) 2.1381(14) 2.2080(10) 2.211(3) 2.209(2)
M(1)-O(1) 1.881(5) 1.907(3) 2.072(2) 2.068(9) 2.077(5)
M(1)-N(1) 1.931(6) 1.936(4) 2.074(3) 2.117(8) 2.080(6)
Bond Angle
C(1)-M(1)-O(1) 172.7(3) 171.03(17) 177.06(13) 176.4(3) 175.4(3)
P(1)-M(1)-C(1) 86.7(2) 88.65(15) 88.23(11) 90.0(3) 88.5(3)
O(1)-M(1)-N(1) 94.2(2) 93.71(13) 88.47(10) 89.6(3) 90.9(2)
P(1)-M(1)-O(1) 86.50(15) 82.38(10) 89.18(7) 86.4(2) 86.91(16)
P(1)-M(1)-N(1) 178.20(18) 172.58(12) 177.27(8) 174.2(2) 177.82(17) a Estimated standard deviations are given in parentheses.
41
Figure 2.5. Thermal ellipsoid representation of Ni(1/2Sal-NO2)PPh3, 1a, showing 50% probability.
42
Such positioning allows these groups to effectively shield the axial faces of the metal
center to enhance the rate of enchainment relative to chain transfer.9, 28 The positioning
is also in accord with the solution spectroscopic data where two sets of doublets are
observed for the terminal isopropyl hydrogens in the 1H NMR spectrum. The Ni-C bond
distance was found to be nearly identical to that observed in 1e, having a value of
1.893(3) Å. Consistent with the Ni-P bond distance of 1e (i.e., 2.172(2) Å) in 1a, the
distance associated with this bond was found to be 2.1754(8) Å, indicating little steric
interaction of large groups in the R1 position with PPh3.
Using the same crystal growth technique as described for 1a, suitable crystals for
X-ray analysis of several of the other derivatives were obtained. The thermal ellipsoid
drawings of two such complexes (2a and 4a) are shown in Figures 2.6 and 2.7,
respectively. Crystallographic data, and selected bond lengths and angles are tabulated
in Table 2.3 and Table 2.4, respectively. Similar to the solid state structure of 1a and 1e,
these complexes adopt the typical square planar geometry (e.g., N–M–P angles in 2a and
4a were found to be 173.33(15) and 173.27(8)º). The nickel-carbon bond distance to the
phenyl ligand in 2a at 1.893(6) Å is identical to that seen in complex 1a. Comparing the
Ni–P bond distances in 1a of 2.1754(8) Å to that seen in 2a of 2.1345(18) Å, we notice a
shortening of the bond distance in 2a of approximately 0.05 Å. This decrease in Ni–P
bond length upon going from PPh3 to PTA is consistent with the smaller cone angle
(103º) and more basic nature of PTA as compared to PPh3. The Pd-P bond distance in
4a was found to be 2.199(3) Å, which is slightly shorter than that observed in cis-
43
Figure 2.6. Thermal ellipsoid representation of Ni(1/2Sal-NO2)PTA, 2a, showing 50% probability.
44
Figure 2.7. Thermal ellipsoid representation of Pd(1/2Sal-NO2)PTA, 4a, showing 50% probability.
45
PdCl2(PTA)2 of 2.226(5) Å13. The difference in the Pd-P bond length in 4a vs the
corresponding Ni-P bond distance in 2a of 0.07 Å is less than the covalent radii
difference in nickel and palladium of 0.11 Å. The Pd-C(methyl) bond length was
determined to be 2.024(9) Å in 4a. The solid-state structure of the methoxy derivative,
complex 4b, was also determined and its structure is depicted in the thermal ellipsoid
representation in Figure 2.8. In this instance, the electron donating ability of the OCH3
group is not reflected in the Pd-P bond distance of 2.1995(12) Å, which is the same as
that observed in 4a (Table 2.4). However, the Pd-C bond distance increases by
approximately 0.025 Å. Nevertheless, electron donating effects have been shown to
greatly decreases the activity of the catalyst as evident in a decrease in the reported
turnover number from 253 kg polyethylene . mol Ni for 1a to 13.3 kg polyethylene . mol
Ni for 1b.9a X-ray structural data and thermal ellipsoids representations for the other
closely related (salicylaldiminato)M(methyl)(PTA) derivatives, 3b, 3d, 4c, and 4d are
provided in Table 2.3 Table 2.4, and Figures 2.9, 2.10, 2.11, and 2.12, respectively.
In a few cases during crystal growth over extended periods of time, ligand
redistribution occurred with concomitant formation of the thermodynamically stable
bis(salicylaldiminato) complexes. These crystals are black in color and appear to be
relatively stable in air. The solid-state structure of one such isolated species, 3b', has
been determined by X-ray crystallography. A thermal ellipsoid drawing of 3b' is shown
in Figure 2.13. The Ni-N and Ni-O bond distances observed in complex 3b' of 1.907(3)
and 1.827(3)Å are slightly shorter than the corresponding parameters found in the parent
46
Figure 2.8. Thermal ellipsoid representation of Pd(1/2Sal-OMe)PTA, 4b, showing 50% probability.
47
Figure 2.9. Thermal ellipsoid representation of Ni(1/2Sal-OMe)PTA, 3b, showing 50% probability.
48
Figure 2.10. Thermal ellipsoid representation of Ni(1/2Sal-Cl)PTA, 3d, showing 50% probability.
49
Figure 2.11. Thermal ellipsoid representation of Pd(1/2Sal-Ben)PTA, 4c, showing 50% probability.
50
Figure 2.12. Thermal ellipsoid representation of Pd(1/2Sal-Cl)PTA, 4d, showing 50% probability.
51
Figure 2.13. Thermal ellipsoid representation of Ni(1/2Sal-OMe)2, 3b’, showing 50% probability.
52
(salicylaldiminato)Ni(methyl)(PTA) derivative, 3b, of 1.931(6) and 1.881(5) Å,
respectively. These decreases in bond lengths are anticipated upon loss of the electron
donating phosphine ligand. The formation of such bis complexes is clearly undesirable
in polymerization processes, and has been an issue for SHOP-type systems which utilize
higher temperatures and pressure to produce high molecular weight polyethylene.40
Ethylene Polymerization
The polymerization of ethylene using 1 was first reported in 1998.9 Although
derivatives incorporating large groups in the R1 position of the salicylaldimine (e.g., 1e)
did not require a phosphine scavenger, other active derivatives such as 1a did in fact
necessitate the use of the air-sensitive co-catalyst, Ni(COD)2. Our approach to by-pass
the need for a co-catalyst involves the use of water-soluble phosphines to facilitate the
dissociation process illustrated in Figure 2.14.
[M]-PTA + ethylene
TOLUENE PHASE
WATER PHASE
M = Ni, Pd
TOLUENE PHASE
WATER PHASE
[M]
PTA
Polyethylene
Phosphine Dissociation
Figure 2.14. Polymerization of ethylene using 3/4 in a biphasic toluene/water solvent system.
53
The dissociation of PTA into the aqueous phase would effectively allow the formation of
the active catalyst in the organic phase, initiating the polymerization. Furthermore, upon
PTA dissociation, re-entering of this phosphine into the organic phase would not occur,
since PTA is not soluble in toluene. This was previously quite evident upon failing to
synthesize 2 via a biphasic toluene/water ligand replacement process (vide supra).
Upon attempting to polymerize ethylene at ambient temperature using 2a as
catalysts utilizing a biphasic toluene/water (1/1) solvent system under 8 atm of ethylene
pressure no polymer formation was observed. Raising the temperature to 70ºC resulted
in Ni(0) formation, and analysis of the water phase revealed the presence of the
phosphine oxide, PTA=O. The formation of phosphine oxide has also been observed in
other rhodium and ruthenium catalytic systems.12b
CONCLUDING REMARKS
Herein, we have reported the synthesis of methyl- and phenyl- derivatives of nickel
and palladium salicylaldiminato complexes containing the water-soluble phosphine
(PTA) in excellent yields. These complexes have all been structurally characterized in
the solid-state by X-ray crystallography. Thus far, we have been unproductive in
catalyzing the polymerization of ethylene with (salicylaldiminato)Ni(Ph)(PTA) in a
biphasic medium. This is undoubtedly due to the stability of the Ni-PTA bond, i.e., the
high temperature required to effect phosphine dissociation in this instance.
With regard to this latter point, we have attempted to determine the rate of Ni–PTA
bond dissociation in 2a initially utilizing a large excess (10 equivalents) of PPh3 as
54
incoming ligand. At ambient temperature, as well as at 35ºC, the 31P signal of PTA in 2a
at -57.8 ppm was unaffected over an extended reaction period. On the other hand, a
similar experiment involving the use of the more basic and less sterically hindered
phosphine, PMe3, as entering ligand resulted in immediate displacement of the PTA
ligand at ambient temperature. This latter process is evidently taking place via an
associative mechanism, a common occurrence in square-planar nickel(II) complexes.
Hence, qualitatively it is apparent that the dissociation of PTA from 2a is not a facile
process at modest reaction temperatures.
The slow initiation step when employing complex 2a as catalyst precursor for the
polymerization of ethylene might be overcome by preparing nickel(II) derivatives
bearing other water-soluble phosphines. For example, the water-soluble meta-TPPTS
ligand, which is electronically almost identical to PPh3 and thereby expected to have
similar or enhanced Ni–PR3 dissociation rates, would seem to be quite appropriate.41
Unfortunately, we have thus far been unsuccessful at preparing the meta-TPPTS analog
of complex 2a. This is most likely due to the significantly larger cone angle in meta-
TPPTS of 170º 42 vs that of PPh3 (145º).36 With this in mind, the palladium DAPTA
derivative, 4d-DAPTA, was successfully synthesized by using the same synthetic
methodology. Unfortunately, the 1H NMR spectrum indicates a slightly larger 3JHP
coupling constant of the Pd-CH3 protons to DAPTA when compared to 4d, and is
presumably due to a stronger Pd-P bond in 4d-DAPTA. Suitable crystals of this
complex were obtained by using the same technique employed for all other complexes,
and the crystallographic data is provided in Table 2.3 and 2.4. A thermal ellipsoid
55
representation is shown in Figure 2.15. In the solid state, the Pd-P bond distance found
to be nearly identical to 4d, as is the case for many of the other bond lengths. As is the
case for free DAPTA, the 1H and 13C NMR displays two shifts associated with the
C(O)CH3 protons, indicating a rotation barrier with respect to the N-C(O)CH3 bond.
Furthermore, the bound DAPTA in 4d-DAPTA results in a slight weakening of the
v(C=O) stretch, as is evident by an approximate 50 cm-1 shift to 1605 cm-1 for the
complex.
In principle the approach outlined in Figure 2.14 appears to be fundamentally
sound if a set of suitable conditions can be found. It is probable that employing less
sterically encumbered water-soluble triphenyl phosphine derivatives as ligands will lead
to metal complexes which have similar metal-PR3 bond dissociation energies as metal-
PPh3, thereby making them effective catalysts for this polymerization process.43
56
Figure 2.15. Thermal ellipsoid representation of Pd(1/2Sal-Cl)DAPTA, 4d-DAPTA, showing 50% probability.
57
CHAPTER III
SYNTHESIS AND CHARACTERIZATION OF 3,7-DIACETYL-1,3,7-TRIAZA-5-
PHOSPHABICYCLO[3.3.1]NONANE (DAPTA) AND ITS GROUP 6 AND
GROUP 10 COMPLEXES*
INTRODUCTION Aqueous organometallic chemistry has received much attention in recent years due
to the many advantages an aqueous medium presents to stoichiometric and catalytic
reactions.1 Water's copious and non-toxic nature, along with its distinct physical
properties, makes it an ideal solvent for numerous processes from an industrial point of
view. With regards to its physical properties, its high heat capacity enables it to
effectively distribute heat from exothermic reactions, and its immiscibility with many
organic compounds allows it to serve as part of a biphasic system where products can be
easily separated from water soluble catalysts by a simple extraction process. The latter
procedure is the foundation of the Ruhrchemie-Rhône Poulenc hydroformylation process
of lower molecular weight olefins, in which the triply meta-sulfonated triphenyl
phosphine ligand, TPPTS, is used with rhodium as the active metal center.1,2 This and
other tertiary water-soluble phosphines (WSP) have been the most widely used class of
water-soluble ligands in aqueous catalysis due to their neutral donating ability which can
_______________
* Reproduced in part with permission from Darensbourg, D. J.; Ortiz, C. G.; Kamplain, J. W. Organometallics, 2004, In Press. Copyright 2004 American Chemical Society.
58
Effectively stabilize the metal center throughout the catalytic cycles (Figure 3.1).
Furthermore, these phosphines can participate in the reduction of the metal center in
such processes as carbon-carbon bond formation reactions, where group 10 metals, M2+,
are reduced to the active M0 species. Apart from TPPTS, a variety of WSP's have
appeared through the years and their catalytic potential has been investigated. Of main
importance to our work is the water-soluble and air-stable 1,3,5-triaza-7-
phosphaadamantane (PTA) ligand which owes its water-solubility to hydrogen bonding
of the nitrogen atoms to water (Figure 3.1).11 Due to its small cone angle (102º) and
excellent donating ability (comparable to PMe3), it has received much attention as a
potential ligand for catalytic reactions such as in the monophasic412c, d and biphasic512a-
b,32d hydrogenation of alkenes and aldehydes.
In addition, various other derivatives of PTA have also been synthesized but remain
relatively unexplored. For example, the sulfone derivative of PTA, 2-thia-1,3,5-triaza-7-
phosphaadamantane-2,2-dioxide (PASO2) was previously prepared by Daigle44 and its
binding to group 6 metals45 was illustrated in our laboratories. However, to our surprise,
the PASO2 derivative possesses very limited water solubility. Shortly after Daigle’s
initial synthesis of PTA, a series of reactions of PTA similar to those observed for its
hexamethylenetetramine analog were carried out by Siele. These included nitration,46
nitosation,47 and acetylation.48 At that time, it was noted that PTA reacts with acetic
anhydride to provide the acetylated product 3,7-diacetyl-1,3,7-triaza-5-
phosphabicyclo[3.3.1]nonane (1).11d Nevertheless, no other studies of this phosphine,
which we will call DAPTA, have been reported. Due to the need for a larger variety of
59
Ph3-nP
SO3Na
n
Ph3-nPn
N NN
P
O
O
N NN
P
COOH
n = 1 (TPPMS), 2 (TPPDS), 3 (TPPTS) n = 1-3, ortho, meta, or para
PTA DAPTA (1)
Figure 3.1. Examples of water-soluble phosphines.
60
water-soluble phosphines to serve as ligands to low valent metal complexes rendering
them soluble in water, we have chosen to investigate DAPTA for this purpose. Herein,
we report the complete characterization of 1 and its corresponding oxide (2). In
addition, several metal complexes were prepared and characterized in solution by
IR/NMR spectroscopy, and in the solid-state via X-ray crystallography, to assess the
nature of the metal-phosphorus bond. The water-solubility of 1 was measured and
compared with other commonly utilized water-soluble phosphines, including its PTA
analog.
EXPERIMENTAL
Materials and Methods
Unless otherwise indicated, all reactions were carried out under an inert argon
atmosphere using standard Schlenk and drybox techniques. Prior to their use, all organic
solvents were distilled from sodium benzophenone ketyl. In the preparation of 1 and 2,
deionized water was used. Cr(CO)6 and W(CO)6 precursors were purchased from
Aldrich Chemical Co., with the latter being sublimed prior to use. Ni(COD)2 was
purchased from Strem Chemical Co. and used without further purification. PTA and its
oxide were prepared following the literature method.11 Although the preparations of 1
and 2 have been previously described by Siele, the syntheses are included herein for
completeness purposes.11d The salicylaldimine used in the preparation of 4 was prepared
according to the literature procedure.9
61
X-ray data were collected on a Bruker CCD diffractometer and covered more
than a hemisphere of reciprocal space by a combination of three sets of exposures; each
exposure set had a different φ angle for the crystal orientation, and each exposure
covered 0.3º in ω. The structures were solved by direct methods. 1H, 13C, and 31P NMR
data were obtained using a Varian Unity+ 300 MHz NMR instrument. 1H and 13C
chemical shifts were referenced according to the deuterated solvent used. The 31P
chemical shifts were referenced using an external 85% H3PO4 sample. Elemental
analyses were conducted by Canadian Microanalytical Inc.
Preparation of 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA)
(1)11d
In a 250 mL round bottom flask equipped with a dropping funnel, PTA (6.25 g,
39.6 mmol) was dissolved in 80 mL of water. To this solution, maintained at 0˚C, acetic
anhydride (12.1 g, 119 mmol) was added dropwise with stirring over a period of 20
minutes. The solution was allowed to stand for 30 minutes and the solvent was removed
under vacuum, leaving behind a white solid. The product was purified by
recrystallization from acetone and obtained in 47% yield. 1H NMR (300 MHz, CDCl3,
δ): 1.96 (s, 6H, C(O)CH3), 4.12 (d, 4JCP = 9.3 Hz, 4H, NCH2N), 4.67 (d, 2JCP = 13.2 Hz,
2H, PCH2N), 4.85 (d, 2JCP = 13.2 Hz, 2H, PCH2N), 5.63 (d, 2JCP = 13.8 Hz, 2H, PCH2N).
13C NMR (75 MHz, CDCl3, δ): 20.9 (C(O)C), 62.03 (N-C-N), 67.0 (P-C-N), 70.1 (P-C-
N), 169.0 (C(O)). 31P (121 MHz, CDCl3, δ): -78.5. IR(νC=O): 1642 cm-1 (CH2Cl2), and
1608 cm-1 (H2O).
62
Preparation of 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane 5-oxide
(2)11d
The preparation of 2 was achieved by the acylation of PTA oxide using an
analogous synthetic protocol as employed for the synthesis of 1, in a 41% yield. Similar
to 1, the ligand readily dissolves in water and polar organic media such as methylene
chloride and THF. 1H NMR (300 MHz, CDCl3, δ): 2.11 (s, 6H, C(O)CH3), 3.27 (m,
2JHH=16.2 Hz, 4JHP=6.60 Hz, JHH=3.22 Hz, 1H), 3.74 (d, 2JHH=7.20 Hz, 2H), 3.81 (dd,
JHP=7.50 Hz, JHH=3.00 Hz, 1H), 3.87 (d, 2JHH=14.4 Hz, 1H), 4.40 (t, 2JHH=14.4 Hz, 1H),
4.87 (d, 2JHH=14.1 Hz, 1H), 5.50 (t, 2JHH=16.2 Hz, 1H), 5.71 (d, 2JHH=14.4 Hz, 1H). 13C
NMR (75 MHz, D2O, δ): 21.7 (d, 3JCP=22.9 Hz, N-C-N), 42.0 (d, 1JCP=67.1 Hz, P-C-N),
46.7 (d, 1JCP=64.1 Hz, P-C-N), 53.4 (d, 1JCP=62.2 Hz, P-C-N), 62.0 (d, 4JCP=6.86 Hz,
C(O)CH3), 66.9 (d, 4JCP=6.49 Hz, C(O)CH3), 169.5 (C(O)), 170.1 (C(O)). 31P NMR
(121 MHz, CDCl3, δ): 2.20.
Preparation of Ni(DAPTA)4 (3)
To a Schlenk flask containing Ni(COD)2 (0.120 g, 0.436 mmol), in approximately
20 mL of toluene, was added 1 (0.400 g, 1.75 mmol), in 5 mL of methanol, via cannula.
The resulting clear solution was stirred for 3 hrs, leading to the formation of a white
precipitate. The white solid was collected by filtration, washed with 2 x 5 mL of ether,
and dried under vacuum. Yield: 94.1%. 1H NMR (300 MHz, CD2Cl2, δ): 2.09 (s, 12 H,
C(O)CH3), 2.13 (s, 12 H, C(O)CH3), 3.11 (d, 1JHH=14.4 Hz, 4H, NCHN), 3.48 (s, 8H,
PCH2N), 3.69 (d, 1JHH=15.3 Hz, 4H, PCHNC(O)), 4.06 (d, 1JHH=13.8 Hz, 4H,
PCHNC(O)), 4.28 (d, 1JHH=15.0 Hz, 4H, NCHN), 4.65 (d, 1JHH=14.1 Hz, 4H,
63
PCHNC(O)), 4.99 (d, 1JHH=14.1 Hz, 4H, PCHNC(O)), 5.25 (d, 1JHH=15.0 Hz, 4H,
NCHN), 5.82 (d, 1JHH=14.4 Hz, 4H, NCHN). 13C NMR (75 MHz, CD2Cl2, δ): 21.5
(C(O)CH3), 22.2 (C(O)CH3), 46.4 (N-C-N), 51.3 (N-C-N), 56.4 (P-C-N), 62.4 (P-C-
NC(O)), 67.7 (P-C-NC(O)), 169.4 (C(O)), 169.8 (C(O)). 31P NMR (121 MHz, CD2Cl2,
δ): -28.3. IR(CH2Cl2): 1643 cm-1 (v(C=O)). Elem. Anal. Calcd. for C36H64N12O8P4Ni:
C, 44.34%; H, 6.56; N, 17.24%; Found: C, 44.77%; H, 6.57%; N, 16.65%.
Preparation of Palladium Salicylaldiminato DAPTA Complex (4)
To a 50 mL Schlenk flask containing (TMEDA)Pd(CH3)2 (150 mg, 0.594 mmol) in
10 mL of toluene at –30ºC, DAPTA (136 mg, 0.594 mmol) in 5 mL of methanol was
introduced via cannula. To this mixture, the salicylaldimine (208 mg, 0.594 mmol) in
10mL of toluene at -30ºC was slowly cannulated into the flask, and the solution was
stirred for 30 minutes. The temperature was raised to room temperature, and the light
red solution was further stirred overnight. Subsequently, the solvent was removed in
vacuo until approximately 5 mL remained, and 20 mL of cold
(-78ºC) pentane was added, resulting in the formation of a yellow precipitate. The solid
was collected by cold cannula filtration and washed (3 x 5 mL) with cold (-78ºC)
pentane, affording 4 in 96.8% yield. 1H NMR (300 MHz, C6D6, δ): -0.14 (d, 3JHP=3.60
Hz, 3H, Pd-CH3), 0.97 (dd, 3JHH=6.60 Hz, 3JHH=2.70 Hz, 6H, CH(CH3)2), 1.29 (dd,
3JHH=6.60 Hz, 3JHH=6.00 Hz, 6H, -C(O)CH3), 1.80 (d, 3JHH=6.60 Hz, 6H, CH(CH3)2),
2.97 – 3.02 (m, 1H, DAPTA), 3.24 – 3.34 (m, 5H, DAPTA), 3.51 (d, 3JHH=14.10, 1H,
DAPTA), 3.62 – 3.67 (m, 1H, DAPTA), 4.21 (d, 3JHH=13.80 Hz, 1H, DAPTA), 4.23 –
4.51 (m, 1H, DAPTA), 6.75 (d, 3JHH=2.7 Hz, 1H, Ar), 7.11 – 7.15 (m, 2H, Ar), 7.48 (d,
64
3JHH=2.7 Hz, 1H, Ar), 7.55 (d, 4JHP=11.4 Hz, 1H, HC=N). 13C NMR (75 MHz, C6H6, δ):
-7.65 (d, 2JCP=12.2 Hz, Pd-CH3), 21.09, 22.78, 24.56, 28.23, 37.28 (d, 1JCP=22.05 Hz, P-
C-N), 41.97 (d, 1JCP=19.73 Hz, P-C-N), 47.13 (d, 1JCP=24.30 Hz, P-C-N), 61.50 (d,
4JCP=4.50 Hz, C(O)CH3), 66.61 (d, 4JCP=4.50 Hz, C(O)CH3), 116.63, 119.75, 123.60,
123.68, 125.53, 127.06, 128.40, 128.74, 129.17, 133.49, 134.44, 140.69 (d, 3JCP=9.15
Hz, C=N), 146.91, 168.46 (C=O), 169.23(C=O). 31P NMR (121 MHz, C6D6, δ): -24.12.
IR (CH2Cl2): v(C=O)=1605 cm-1. Elem. Anal. Calcd. for C29H39N4O3PCl2Pd: C,
49.79%; H, 5.57; N, 8.01%; Found: C, 51.96%; H, 5.81%; N, 7.66%.
Preparation of M(CO)5(DAPTA) (M = W (5), Cr (6)) Complexes
The replacement of a single CO molecule was achieved by the photochemical
reaction of M(CO)6 in THF. After photolyzing W(CO)6 (0.200 g, 0.57 mmol), in 100
mL of THF, this solution was cannulated over to a flask containing 1 (0.130 g, 0.57
mmol), in 10 mL of THF. The resulting solution was stirred for 1 hr followed by
removal of the solvent in vacuo. The solid was sublimed to remove any excess W(CO)6.
The synthesis of 6 was achieved in an analogous manner. Both complexes are colorless
and were cystallized and isolated by the slow evaporation of THF from the
corresponding solution, resulting in good yields (>80%). Complexes 5 and 6 are
insoluble in water and non-polar organic solvents (e.g., hexane, pentane), but readily
dissolve in polar media (e.g., chloroform, THF).
(5) 13C NMR (75 MHz, CD2Cl2, δ): 195.19 (t, dd, 1JCW=127.75 Hz, 2JCP=7.16
Hz, CO (trans)), 199.07 (d, 2JCP=21.19 Hz, CO (eq)). 31P NMR (121 MHz, CD2Cl2, δ): -
47.7 (t, 1JPW=228.52 Hz). Elem. Anal. Calcd. for C14H16N3O7PW: C, 30.40%; H, 2.92%;
65
N, 7.60%; Exp.: C, 30.30%; H, 2.94%; N, 7.57%. IR(CHCl3, cm-1): 1650 (νC=O,
DAPTA), 1944 (E), 2076 (A1).
(6) 31P NMR (121 MHz, CD2Cl2, δ): -5.79. Elem. Anal. Calcd. for
C14H16N3O7PCr: C, 39.92%; H, 3.83%; N, 9.97%; Exp.: C, 40.09%; H, 3.85%; N,
9.98%. %. IR(CHCl3, cm-1): 1658 (νC=O, DAPTA), 1940 (E).
Water-Solubility of 1
The extent of water solubility of 1 was assessed by placing a small, accurately
weighed quantity of the ligand in a vial followed by the slow addition of water via a
100µL syringe with stirring. In a typical experiment, 75 µL of water was needed to
completely dissolve 100 mg of 1. Solubility measurements were repeated several times
to yield an average value for the molar solubility of 1 in water of 7.4 M.
RESULTS AND DISCUSSION
The synthesis of DAPTA and other PTA derivatives was first reported by Siele in
1977.11d The ligand is easily prepared by direct acylation of PTA in water with acetic
anhydride at 0˚C (eq. 3.1).
NN
N
P
+
O
O OH2O, r.t.20 min N
NN
PO
O
(1)
(3.1)
66
Surprisingly, the water-solubility of DAPTA was found to be approximately 7.4 M,
making it one of the most water-soluble phosphile ligands thusfar reported.1 A
comparison of the water solubility of 1 to its parent, PTA, and the sulfonated
triphenylphosphine derivatives (i.e., TPPMS and TPPTS)31 illustrates its superior water-
solubility characteristic (Figure 3.2). Additionally, the ligand readily dissolves in
common organic solvents such as methylene chloride, acetone, and alcohols (e.g.,
methanol and ethanol), making it a very versatile ligand which may be used in a variety
of solvents.
The previously reported NMR data for 1 by Siele were obtained on a 60 MHz
instrument, and therefore, no detailed splitting patterns or coupling constants were
provided. Here, we wish to point out some of these key features by examining the 1H,
13C, and 31P spectra of the phosphine. All of the 1H NMR resonances associated with the
methylene carbons exhibit phosphorus coupling (xJHP, x = 2,4) on the order of 13 Hz.
The methyl hydrogens on the acyl functionality (C(O)CH3) are observed as a singlet at
1.96 ppm. In the 13C NMR spectrum, the acyl carbons NC(O)CH3 are displayed by a
single resonance at 168.96 ppm, which is contrary to what is expected. That is, the two
acyl groups adopt an anti conformation in the solid-state (vide infra) with the barrier to
rotation of the N-C(O) bond generally ascribed to the π electronic resonance model of an
amide(A and B in Scheme 3.1).49a This experimental rotational barrier is expected to be
about 18-19 kcal/mol.49b-d More recent ab initio computations assign a large part of the
67
Figure 3.2. Molar water-solubility of selected tertiary water-soluble phosphines.
7.4
1.941.5
0.22
0
1
2
3
4
5
6
7
8
DAPTA TPPTS PTA TPPMS
Water-Soluble Phosphines
Mol
arity
(mol
/L)
68
Scheme 3.1
rotational stability of the N–C bond to a coulombic interaction via the σ system between
the N and carbonyl C atoms(C in Scheme 3.1).4e Further upfield are the resonances
pertaining to the P-C-N carbons, which fall at 67.0 and 70.1 ppm, respectively. Those
associated with the N-C-N carbons are found at 62.0 ppm.
Upon dissolving 1 in CH2Cl2 and allowing the slow diffusion of pentane into the
solution over several days at -20ºC, resulted in quality crystals for X-ray diffraction.
The crystallographic data and selected bond distances and angles are presented in Table
3.1 and Table 3.2, respectively. A thermal ellipsoid representation of 1 is shown in
Figure 3.3. In the solid state, the C(O)CH3 groups are anti with respect to each other.
The N(2)-C(6) and N(3)-C(7) bond distances were found to be short when compared to
other N-C bond distances with values of 1.373(18) and 1.377(18) Ả, respectively, and
resembles a Schiff base (N=C) double bond (Scheme 3.1). The P(1)- C(1) bond distance
was found to be approximately 0.03 Å longer than the P(1)-C(2) counterpart, but is
nevertheless significantly shorter than that found in the P-C bond lengths of PTA (i.e.,
1.857(3) Ả).11c
N
O
N
O
N-C+
O
A B C
69
Table 3.1. Crystallographic data for compounds 1, 2, 5, and 6.
1 2 5 6
Cryst syst monoclinic orthorhombic monoclinic orthorhombic
space group P2(1) Pbca P2(1)/c Pbca
V, Å3 535.3(11) 2224(4) 1843.8(7) 3633(7)
Z 2 8 4 8
a, Å 6.191(7) 8.506(10) 12.000(2) 11.836(13)
b, Å 10.431(12) 11.121(13) 12.922(3) 13.693(14)
c, Å 8.407(10) 23.51(3) 13.238(3) 22.41(2)
β, deg 99.59(2) — 116.076(4) —
T, K 110 110 110 110
d(calc), g/cm3 1.422 1.465 1.993 1.541
Abs coeff, mm-1 0.242 0.245 6.393 0.759 R,a % [I > 2σ (I)] 10.59 6.17 5.26 3.09
Rw,a % 19.23 6.86 6.49 4.66 a R = Σ || Fo | – | Fc || / ΣFo and RwF = {[Σw(Fo – Fc)2] / ΣwFo
2}½
70
Table 3.2. Selected bond distances (Å) and angles for compounds 1, 2, 5, and 6.a
Compound 1
P(1)-C(1) 1.736(15) N(2)-C(6) 1.373(18) N(3)-C(7) 1.377(18) P(1)-C(2) 1.707(14) C(6)-O(1) 1.224(15) C(7)-O(2) 1.258(14) P(1)-C(3) 1.742(14) C(6)-C(8) 1.524(19) C(7)-C(9) 1.483(19) P(1)-C(1)-N(2) 118.5(9) C(1)-N(2)-C(6) 116.0(10) P(1)-C(2)-N(3) 119.9(10) C(2)-N(3)-C(7) 124.7(11) P(1)-C(3)-N(1) 115.0(10)
Compound 2 P(1)-C(1) 1.816(3) N(2)-C(6) 1.365(4) N(3)-C(7) 1.360(4) P(1)-C(2) 1.827(3) C(6)-O(1) 1.227(4) C(7)-O(2) 1.236(4) P(1)-C(3) 1.797(3) C(6)-C(8) 1.500(5) C(7)-C(9) 1.499(4) P(1)-O(3) 1.492(3) P(1)-C(1)-N(2) 111.80(18) C(1)-N(2)-C(6) 118.5(2) P(1)-C(2)-N(3) 114.57(19) C(2)-N(3)-C(7) 123.3(2) P(1)-C(3)-N(1) 106.19(18)
Complex 5 P(1)-C(1) 1.840(11) N(2)-C(6) 1.344(13) N(3)-C(7) 1.348(13) P(1)-C(2) 1.849(10) C(6)-O(1) 1.224(13) C(7)-O(2) 1.230(12) P(1)-C(3) 1.845(11) C(6)-C(8) 1.535(15) C(7)-C(9) 1.519(15) W(1)-P(1) 2.492(3) W(1)-C(11) 2.053(13) W(1)-C(13) 2.032(13) W(1)-C(10) 2.049(14) W(1)-C(12) 1.999(13) W(1)-C(14) 2.040(13)
71
Table 3.2 (Continued).
Compound 5 P(1)-C(1)-N(2) 117.6(7) C(1)-N(2)-C(6) 119.1(9) P(1)-C(2)-N(3) 112.4(7) C(2)-N(3)-C(7) 124.5(9) P(1)-C(3)-N(1) 109.8(7) C(10)-W(1)-P(1) 176.1(3) C(11)-W(1)-P(1) 90.0(3) C(10)-W(1)-C(11) 88.3(4) C(12)-W(1)-P(1) 92.7(4) C(10)-W(1)-C(12) 90.8(5)
Compound 6 P(1)-C(1) 1.853(3) N(2)-C(6) 1.359(4) N(3)-C(7) 1.359(4) P(1)-C(2) 1.839(3) C(6)-O(1) 1.233(4) C(7)-O(2) 1.227(4) P(1)-C(3) 1.836(3) C(6)-C(8) 1.504(5) C(7)-C(9) 1.512(5) Cr(1)-P(1) 2.3562(19) Cr(1)-C(11) 1.910(4) Cr(1)-C(13) 1.902(4) Cr(1)-C(10) 1.863(4) Cr(1)-C(12) 1.902(4) Cr(1)-C(14) 1.903(4) P(1)-C(1)-N(2) 113.8(2) C(1)-N(2)-C(6) 124.7(3) P(1)-C(2)-N(3) 114.93(19) C(2)-N(3)-C(7) 118.2(2) P(1)-C(3)-N(1) 109.9(2) C(10)-Cr(1)-P(1) 173.55(10) C(11)-Cr(1)-P(1) 89.31(12) C(10)-Cr(1)-C(11) 87.37(15) C(12)-Cr(1)-P(1) 94.56(11) C(10)-Cr(1)-C(12) 91.00(14) a Estimated standard deviations are given in parenthesis.
72
Figure 3.3. Thermal ellipsoid representation of DAPTA (1) showing 50% probability.
73
As evident from the space filling model, the rigid nature of the ligand creates a
cavity within the cage structure (Figure 3.4). The phosphorus atom is clearly exposed,
allowing for easy binding to a metal center. Additionally, the acyl-free nitrogen and
oxygen atoms are also exposed, which facilitates hydrogen bonding to the surrounding
aqueous environment. The calculated cone angle was found to be similar to that
reported for PTA, having a value of about 102º. The phosphine oxide species 2 was also
fully characterized in solution and in the solid state. This derivative is easily prepared
from PTA oxide employing the same synthetic strategy used in the synthesis of 1 (eq.
3.2).
N NN
P
O
+
O
O OH2O, r.t.20 min. N N
N
P
O
O
O
2
(3.2)
Spectroscopically, 2 is similar to its parent. Although difficult to interpret, the 1H NMR
spectrum displays coupling between geminal hydrogens. For example, the proton (HA),
associated with the N-CH-N framework and in the axial position, is shielded more by the
syn C=O group residing on the adjacent nitrogen and therefore is located further
downfield at 5.71 ppm. Meanwhile, its geminal hydrogen, residing in the equatorial
position, is less shielded and appears further upfield with a common 2JHH coupling
74
(a) (b)
Figure 3.4. Space filling model of DAPTA (1) showing (a) front and (b) side view.
75
constant (i.e., 14.4 Hz) (Figure 3.5).
Figure 3.5. Shielding effects on geminal protons by acyl group in DAPTA oxide (2).
31P coupling is observed for the P-CH2-N protons, located at 3.27 ppm, and is on the
order of 6.60 Hz. Similar to 1, the 13C NMR spectrum is also easy to interpret, and
displays several signals with 31P coupling. For example, the P-C-N carbons are located
at 41.99, 46.72, and 53.40 ppm with 1JCP constants of 62-67 Hz. The coupling between
these hydrogens and phosphorus illustrates the pronounced electronic effect of oxygen.
To further illustrate this effect, the C(O)CH3 carbons also exhibit phosphorus coupling,
four bonds away. This is not observed in 1. The two C=O signals reside at 169.45 and
170.09 ppm with an absence of 31P coupling.
Allowing a concentrated CH2Cl2 solution of 2 to stand at -20˚ C over a period of
two weeks resulted in the formation of large, colorless, single crystals. Using these
crystals for X-ray analysis, a solid state structure of 2 was obtained. Crystallographic
data, and selected bond distances and angles are provided in Table 3.1 and Table 3.2,
respectively. A thermal ellipsoid representation of 2 is shown in Figure 3.6. A key
N N
N
P
O
OHA
HB
More shieldedappears higher downfieldthan HB
O
76
Figure 3.6. Thermal ellipsoid representation of DAPTA oxide (2) showing 50% probability.
77
feature in the solid state, as was also observed in complexes 5 and 6, are the P(1)-C(Y)
(Y = 1-3) bond distances. Upon coordination of the ligand to a metal or in its oxidized
form, these bond lengths are approximately 0.09 Å longer than those observed in 1.
However, the N(2)-C(6) and N(3)-C(7) are nearly identical when compared to its parent,
as is the case for many of the other bond distances. The P(1)-O(3) bond distance is
found to have a value of 1.492(3) Å. In the space filling model, the ligand also
possesses the cavity observed in 1 with the oxygen atom coordinated to phosphorus fully
exposed for binding (Figure 3.7). The other oxygen atoms as well as the acyl-free
nitrogen is also exposed, similar to 1.
Several complexes incorporating 1 were synthesized to illustrate the binding
mode and strength of this phosphine. PTA complexes of group 10 metals have been
previously reported and were found to be readily soluble in water. Of main interest is
the nickel(0) PTA complex, Ni(PTA)4, which can be synthesized from Ni(COD)2 and
four equivalents of PTA in a toluene/methanol solution. Using this methodology, the
Ni(DAPTA)4 (3) derivative was prepared (eq. 3.3).
Ni(COD)2 + 4 DAPTA Ni(DAPTA)4 + 2 CODtoluene/methanol
2 hr, r.t. 3 (3.3)
The product was characterized by 1H, 13C, and 31P NMR as well as elemental analysis.
Unfortunately, 3 is not soluble in water or alcoholic solvents such as methanol or
ethanol, but is readily soluble in chlorinated organic solvents such as methylene
78
(a) (b)
Figure 3.7. Space filling model of DAPTA oxide (2) showing (a) front and (b) side view.
79
chloride. The insoluble nature of the complex in water is surprising due to the high
water-solubility of 1 and Ni(PTA)4 (0.291 M).13 The IR spectrum displays the v(C=O)
stretch at 1643 cm-1 which is nearly identical to the v(C=O) stretch of the free ligand in
CH2Cl2. The 13C NMR spectrum displays the two signals due to the acyl carbons at
169.8 and 169.4 ppm, respectively, while the 1H NMR contains many signals that are
split by phosphorus and geminal coupling. Attempts to grow suitable crystals in CH2Cl2
have failed due to the formation of spherical crystals, all of which did not diffract upon
exposure to X-ray radiation.
Another group 10 metal complex bearing 1 is the salicylaldiminato palladium
complex 4 (see Chapter II). This derivative was prepared using the synthetic
methodology employed for the synthesis of palladium salicylaldiminato PTA complexes
(eq. 3.4).
N
NPd
i-Pr
i-PrN
HO
Cl
Cl
++ DAPTA1. -30ºC, 30 min2. r.t., overnight-CH4, -TMEDA
O
Cl
Cl
N
i-Pr
i-Pr
PdDAPTA
CH3
Toluene/MeOH
(3.4)
In solution, the complex is very similar to its PTA analogue. For example, the aldimine
hydrogen, HC=N exhibits 4JHP coupling on the order of 11.4 Hz, which is slightly larger
than that reported for the PTA analogue (i.e., 10.5 Hz). The isopropyl groups on the
aniline moiety are perpendicular to the plane and exhibit a rotation barrier, as two sets of
signals are observed in the 1H NMR spectrum for the CH(CH3)2 hydrogens. The ν(C=O)
80
stretch was found to be located at 1605 cm-1, which is approximately a 50 cm-1 shift to
lower frequency from that of the free ligand. Additionally, a rotation barrier exists about
the N-C(O)CH3 bonds as two sets of signals are observed in the 13C NMR spectrum for
the C(O)CH3 groups.
Allowing the slow diffusion of pentane into a toluene solution of 4 at -20˚C resulted
in X-ray quality crystals. Crystallographic data and selected bond distances and angles
are tabulated in Table 2.2 and Table 2.3 (labeled as 4d-DAPTA in Chapter II),
respectively. A thermal ellipsoid representation of 4 is presented in Figure 2.15. The
solid state structure of the complex is nearly identical to its PTA analogue, with the
Pd(1)-P(1) bond distances being the same in both complexes (i.e., 2.209(2) and 2.211(3)
Å for 4 and the PTA analogue , respectively). The palladium metal center adopts the
standard square planar geometry as the C(1)-Pd(1)-O(1) and P(1)-Pd(1)-N(1) bond
angles are found to have values of 175.4(3) and 177.82(17)º, respectively.
Group 6 pentacarbonyl complexes of DAPTA were also prepared by the typical
reaction protocol of photolyzing a THF solution of M(CO)6 (M= W, Cr) to produce the
M(CO5)(THF) intermediate. Following the in situ formation of M(CO)5(THF), a THF
solution of 1 was added, yielding the M(CO)5(DAPTA) (M = W (5), Cr (6)) complexes
in good yields (eq. 3.5).
81
(3.5)
For the tungsten derivative, 5, the v(C=O) stretch associated with bound 1 was found to
be located at 1663 cm-1 in THF, a 10 cm-1 shift to higher energy when compared to the
free ligand. In the 195-200 ppm region of the 13C NMR, the two signals pertaining to
the M–CO carbons are observed with pronounced 31P and 183W coupling. The signal at
195.2 ppm, due to the equatorial carbonyls, has a 1JCW and 2JCP coupling of 127.8 and 7.3
Hz, respectively. The resonance at 199.1 ppm, derived from the axial carbonyl, exhibits
a 31P coupling of 21.2 Hz with no visible 183W coupling due to the lower signal intensity.
The 31P resonance is located at -47.7 ppm, an approximate 25 ppm upfield shift from the
free ligand, with 1JPW coupling of 228.5 Hz, which is similar to that observed for the
W(CO)5(PTA) (1JPW = 218.2 Hz) and W(CO)5(PASO2) (1JPW = 228.9 Hz) complexes.45a
Colorless crystals suitable for X-ray diffraction were isolated by the slow
evaporation of THF from a corresponding solution of the complex at room temperature.
Crystallographic data, and selected bond distances and angles for the complex is
presented in Table 3.1 and Table 3.2, respectively. A thermal ellipsoid representation of
M(CO)6(1) hv, THF(2) 1, THF, 1hr, r.t.
N NN
P
O
O
MOC COCOOC
CO
M=W (5) Cr (6)
82
the complex showing 50% probability is shown in Figure 3.8. The tungsten metal center
exhibits a slightly distorted octahedral coordination with the C(12)-W(1)-C(13), C(10)-
W(1)-P(1), and C(11)-W(1)-C(14) bond angles having values of 179.7(5), 176.1(3), and
177.3(5)˚ , respectively. The pronounced shorter W-Ceq bond distance observed for the
axial carbonyl in the W(CO)5(PTA) and W(CO)5(PASO2) complexes is not observed in
5.45a All W–C bond distances have an average value of 2.044 Å. The W(1)-P(1) bond
distance is very similar to the PTA analog with a value of 2.492(3) Å, and is shorter than
the W-P distance of 2.516 Å of the trimethylphosphine analogue, W(CO)5(PMe3).50a
Using the same crystal growth technique, crystals of 6 suitable for X-ray analysis
were obtained. Crystallographic data, and selected bond distances and angles are
presented in Table 3.1 and Table 3.2, respectively. A thermal ellipsoid representation
showing 50% probability of the complex is provided in Figure 3.9. The chromium metal
center exhibits a slightly distorted octahedral geometry with the C(12)-Cr(1)-
C(13),C(10)-Cr(1)-P(1), and C(11)-Cr(1)-C(14) bond angles having values of
175.55(14), 173.55(10), and 177.30(14)˚, respectively. Although not observed in 5, the
axial Cr(1)-C(10) distance is appreciably shorter than the equatorial Cr-CO with a value
of 1.863(4) Å. This is approximately 0.04 Å shorter than the average Cr-C bond
distance pertaining to the equatorial carbonyls. The Cr(1)-P(1) bond distance was found
to be 2.3562(19) Å, which is approximately 0.01Å shorter than that found in the
Cr(CO)5PMe3 analogue.50b,c Furthermore, the pronounced tilt associated with the
phosphine ligand and the equatorial carbonyl plane observed for the PTA and PASO2
tungsten pentacarbonyl derivatives is not present in complex 5 and 6.45a
83
Figure 3.8. Thermal ellipsoid representation of W(CO)5(DAPTA) (5) showing 50% probability.
84
Figure 3.9. Thermal ellipsoid representation of Cr(CO)5(DAPTA) (6) showing 50% probability.
85
CONCLUDING REMARKS
The cage-opening reaction of PTA and its oxide with acetic anhydride to provide
the corresponding acylated products 1 and 2, respectively, has been revisited. In this
report we have fully characterized these derivatives in solution by 1H/13C/31P NMR and
infrared spectroscopies, as well as in the solid-state by X-ray crystallography. As
anticipated, restricted rotation about the amide nitrogen–carbonyl carbon bond is
observed which is consistent with the short N–C(O) bond distances determined in these
derivatives. Phosphine 1 was shown to possess excellent solubility in water (7.4 M),
much greater than that of its PTA analog. In accordance with the water solubility of 1,
its νC=O vibration in water occurs at 1608 cm-1, some 34 cm-1 to lower energy than that
observed in weakly interacting organic solvents. This is indicative of a strong
interaction of the amide nitrogen–CO bond dipole with water.
The binding ability of DAPTA (1) toward a variety of metal centers was shown to
be very much comparable to that of the parent PTA ligand, which in turn compares
favorably with the air-sensitive PMe3 ligand. This is evident in the M–P bond distances
observed in corresponding metal complexes of 1 and PTA. For example, the W–P bond
distances in (CO)5W(PTA), (CO)5W(DAPTA), and (CO)5WPMe3 are 2.4976(15),
2.492(3), and 2.516(3) Å, respectively. Further evidence for the relative binding abilities
of 1 and PTA was provided by the similarities in the ν(CO) vibrational modes in
M(CO)5L derivatives, where M = Cr or W and L = 1 or PTA.51 Unexpectedly, the
Ni(DAPTA)4 (3) derivative, which is highly soluble in organic solvents, exhibits no
solubility in water, whereas its Ni(PTA)4 analog is very water soluble. We will continue
86
our efforts to obtain X-ray quality crystals of this derivative in hopes that its solid-state
structure will shed some light on this puzzling issue. Finally, it should be possible to
synthesize other phosphine ligands via this cage-opening reaction which possess a wide
range of solubility and metal-binding properties.45b
87
CHAPTER IV
DEVELOPMENT OF NOVEL CHROMIUM SALEN CATALYSTS FOR THE
COPOLYMERIZATION OF CO2 AND EPOXIDES*
INTRODUCTION
The search for alternate, more benign and cost effective processes which would
replace those dealing with hazardous substances or higher cost systems is of great
interest to many laboratories worldwide. A prime example is the industrial production
of polycarbonate which is currently produced by the interfacial condensation of
phosgene and diols (e.g., bisphenol-A).16 The inherit hazards associated with this
system has led to increased research in this area. An alternative is the transition metal-
mediated route involving the catalytic coupling of CO2 and aliphatic epoxides (e.g.,
cyclohexene oxide (CHO), propylene oxide (PO), and ethylene oxide). The obvious
advantage to this process is the handling of less toxic monomers via the elimination of
phosgene. In addition, the use of CO2 as a monomer is of great interest due to its
economic implications, copious nature, and non-toxic characteristic.18 The harboring of
this small molecule for this purpose was first envisioned by Inoue in 1969, whereby a
heterogeneous zinc system was employed to afford high molecular weight copolymers.17
However, large catalyst loadings, reproducibility issues, low yields, and its
heterogeneous nature were major drawbacks and improvements were necessary.
_______________
* Reproduced in part with permission from Darensbourg, D. J.; Yarbrough, J. C.; Ortiz, C. G.; Fang, C. C. J. Am. Chem. Soc. 2003, 125, 7586. Copyright 2003 American Chemical Society.
88
Following Inoue's discovery, several hetero- and homogeneous catalytic systems
have appeared that exhibit superior activities. The first and most active homogeneous
system to that date was realized by Darensbourg and workers in the late 1990's.21b Their
catalyst was comprised of a bulky phenoxide ligand framework coordinated to zinc. For
the most active derivative, TON's and TOF's were on the order of 1441 g polymer . g Zn-
1 and 21 g polymer . g Zn-1 . hr-1, respectively. Further improvements were later
achieved by Coates with the development of a β-diimine zinc catalyst.22 This system is
currently the most active with TOF's on the order of 2290 mol CHO consumed . mol Zn-1
. hr-1. One of the most attractive features involves the mild reaction conditions (e.g., 100
CO2 psi at room temperature) used during polymerization. Other systems that have
appeared are Inoue's25, and Kruper and Dellar's26 aluminum and chromium porphiryn
systems, respectively. In the former, the aluminum catalytic system was found to
effectively copolymerize CO2 and PO as a living polymer with substantial amounts of
ether linkages. The Kruper and Dellar system, on the other hand, predominantly affords
cyclic carbonate, but has the potential to produce copolymer at lower temperatures using
selected epoxides such as CHO. A similarity between both systems is the use of a Lewis
base cocatalyst to significantly enhance catalytic activity. Copolymerizations using
supercritical CO2 have also been carried out with CO2 acting as a solvent and monomer
using a soluble fluorinated chromium porphyrin catalyst.52
Recently, our laboratories reported the use of a Cr(salen)Cl catalyst for the
copolymerization of CO2 and CHO.23 The catalyst produces copolymer with activities
on the order of 28.5 g polymer . g Cr-1 . hr-1, and similar to the aluminum and chromium
89
porphyrin systems, is enhanced by the addition of a Lewis base (i.e., N-methyl
imidazole). By varying the amounts of the cocatalyst, activities as high as 88.2 g
polymer . g Cr-1 . hr-1 are observed. The reaction mixture consisted of predominantly
copolymer with only a small amount of cyclohexene carbonate. Furthermore, the
copolymer exhibited nearly 100% CO2 incorporation with only trace amounts of ether
linkages. Additionally, the catalyst is also effective in the copolymerization of other
epoxides such as [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (TMSO) to produce a
new type of polymeric material which has very distinct physical properties (e.g.,
Tg>180˚C) from the CHO copolymer.53 More importantly, however, is the completely
soluble nature of this epoxide in liquid CO2, providing a monophasic medium as
opposed to the biphasic medium found in the CHO/CO2 copolymerization, and thereby
making it an ideal system for mechanistic studies.54 The mechanism under which
polymer formation occurs is thought to take place via a bimetallic initiation step and first
order enchainment with respect to catalyst. In the former process, the mechanism
proposed by Jacobsen involves two chromium metal centers in which one effectively
delivers the nucleophile and thereby ring-opens the epoxide bound to a second metal
center (Figure 4.1).24
Figure 4.1. Jacobsen's initiation step.
Cr Cl O
R1
R2
Cr ClL
L = epoxide, Lewis Base
90
Propagation, on the other hand, is first order with respect to catalyst and is thought to
occur via the weak interaction of an oncoming epoxide to the metal center followed by
ring-opening by the bound alkoxy group.23 The use of a Lewis base creates a more
nucleophilic alkoxy group, resulting in a faster ring-opening step. The drawback,
however, involves an induction period associated with the Lewis base competing with
epoxide for the open site in the bimetallic initiation step.
Herein, we wish to report the synthesis of Cr(salen)X catalysts bearing different
initiators (Figure 4.2). The activities and induction periods associated with these
catalysts in the copolymerization of CO2 with CHO, PO, and TMSO in the presence of
strongly electron donating phosphines are described. The terpolymerization of
TMSO/CHO and TMSO/PO with CO2 system is also presented. A mechanism for the
copolymerization based on the aforementioned information is also proposed, and catalyst
design aspects are also considered by the synthesis of other related chromium Schiff
base complexes.
EXPERIMENTAL
Materials and Methods
Unless otherwise indicated, all reactions were carried out under an inert argon
atmosphere using standard Schlenk and drybox techniques. Prior to their use, all
solvents were distilled using standard techniques. All reagents, including CrCl3(THF)3,
were purchased from Aldrich Chemical Co. CrPh3(THF)3 was prepared according to the
91
Figure 4.2. Cr(salen)X catalysts for the copolymerization of CO2 and epoxides.
N N
O O
Cr
R1
R2 R2
R1
Y
X
Catalyst X Y R1 R2 1 Br H t-Bu t-Bu 2 Br C6H4 t-Bu t-Bu 3 Br C6H4 H Ph 4 H t-Bu t-BuO
92
literature procedure.55 All salen ligands were prepared from the condensation of the
corresponding commercially available diamine and salisaldehyde in methanol at reflux
conditions. The aldehyde pertaining to a was prepared according to the literature
procedure.33 The salicylaldimine ligands a-c were prepared by the condensation reaction
between the corresponding aldehyde and commercially available 2,6-diisopropyl aniline
(Aldrich Chemical Co.).
1H and 13C NMR data were obtained using a Varian Unity+ 300 MHz NMR
instrument. 1H and 13C chemical shifts were referenced according to the deuterated
solvent used. Infrared data was collected using a Mattson 6021 FTIR spectrometer with
DTGS and MCT detectors.
Copolymerization of CO2 and Epoxides: 24 Hour Reactions
A typical reaction was carried out using the following protocol. A 35 mL glass vial
with a septum was charged with 1 (50 mg, 0.087 mmol) and PCy3 (24.4 mg, 0.087
mmol) followed by the addition of 20 mL of CHO. The solution was then introduced
into a pre-dried (at 80˚C for 8 hr) stainless steel autoclave via an injection port followed
by pressurizing to approximately 550 psi CO2 pressure at room temperature. The
temperature was then raised to 80˚C, at which the CO2 pressure increased to 800 psi.
The reaction was carried out for 24 hr, after which the heat was turned off and the
reactor was allowed to reach room temperature. After venting the excess CO2, the
copolymer was removed from the reactor by dissolution in methylene chloride. The
excess solvent was allowed to slowly evaporate, after which the polymer was dried at
approximately 100˚C under vacuum.
93
The polymer's CO2 content was obtained by 1H NMR spectroscopy, focusing on the
protons adjacent to the carbonate linkages displayed at 4.6 ppm. The protons pertaining
to ether linkages are observed at 3.5 ppm, and an integration of the aforementioned
carbonate and ether linkages provides the percent CO2 incorporation. Additionally, 13C
NMR spectroscopy was used to verify the tacticity of the polymer. An IR spectrum of
the reaction mixture before drying was also obtained to detect any amounts of
cyclohexene carbonate produced during catalysis.
Copolymerization of CO2 and CHO Using 1-5 and Monitored by IR Spectroscopy
To illustrate the procedure used for carrying out a typical reaction, the
copolymerization of CO2 and CHO using 1 as the catalyst is used as an example: To a
35 mL glass vial sealed with a septum was added 10 mL of CHO under argon and
introduced into the high pressure ASI ReactIR 300mL autoclave reactor via an injection
port at 80˚C. A background spectrum was obtained using 128 scans. Next, to a separate
35 mL vial, 1 (75 mg, 0.131 mmol) and PCy3 (36.7 mg, 0.131 mmol) were combined
and dissolved in 10 mL of CHO, and the dark brown solution was subsequently injected
into the reactor at 80˚C. The autoclave was then charged with approximately 800 psi
CO2 pressure. Infrared spectral data was immediately collected every 3 minutes for 12
hr. The profiles associated with the peak at 1750 cm-1 (v(CO2) of copolymer) were
generated after data collection and initial rates were taken as the slope of these plots. The
resulting polymer was also collected and dried by the procedure mentioned above.
94
Synthesis of Cr(salen)X (X = Br, OPh) Complexes (1-4)
A typical procedure involving the synthesis of 1 follows: To a three-neck round
bottom flask, equipped with a nitrogen adapter and a graduated addition funnel and
maintained at -40˚C, using a dry ice/acetone bath, was added CrCl3(THF)3 (1.5 g, 4.00
mmol) which was dissolved in approximately 50mL of THF. To the addition funnel,
commercially available PhMgBr (2.18 g, 12.01 mmol) in THF was added and the
solution was was added dropwise over a 45 minute time period into the purple reaction
mixture. The solution was allowed to come to room temperature and an additional 15
mL of THF was added. The red-brown solution stirred for 4 hr and filtered, after which
the H2Salen (1.97 g, 4.00 mmol), in 10 mL of THF, was cannulated into the solution.
One equivalent of MeOH (0.128 g, 4.00 mmol) was then added via a microliter syringe,
and the dark brown solution was allowed to stir overnight. After this time period, the
solvent was removed and the brown solid was redissolved in 50 mL of benzene and
filtered. Upon removing the solvent, the solid was redissolved in 100 mL of pentane and
filtered. Removal of the solvent resulted in the isolation of 1 in good yields (>80%).
Synthesis of Bis(3-R-salicylaldimine) Chromium(III) Chloride Acetonitrile
Complex (7a)56
The synthesis of the analogous complex, 7b, bearing the 3,5-di-tert-butyl
salicylaldehyde unit has been previously prepared by Gibson.56 Due to the lack of
important details in the literature preparation, we wish to fully describe the synthesis of
7a. To a 50 mL Schlenk flask containing the salicylaldimine (0.40 g, 1.12 mmol), in 25
mL of ether, n-butyllithium (0.7 mL, 1.12 mmol) in hexanes (1.6 M) was added
95
dropwise at -78˚C. The resulting yellow solution was stirred for 2 hr. The solution was
then cannulated over to a 50 mL Schlenk flask containing CrCl3(THF)3 (0.21 g, 0.56
mmol) in 10 mL of THF, producing a green mixture which was allowed to stir overnight.
Purification was achieved by filtration to remove LiCl, and the solvent was then
removed, leaving 6a as a green-brown solid. To a flask containing 6a, approximately 30
mL of acetonitrile was added, and the solution was stirred for 4 hr. Filtration followed
by removal of the solvent yields 7a as a yellow-green solid. Characterization of 7a was
achieved by X-ray crystallography via the use of dark brown crystals formed by the slow
diffusion of pentane into a toluene solution of 7a.
RESULTS AND DISCUSSION
Initially, the synthesis of Cr(salen)(OR) derivatives bearing an alkoxy group as the
initiator was envisioned by reacting the Cr[N(SiMe3)2]357 precursor with one equivalent
of the H2salen ligand and ROH, respectively. However, Cr[N(SiMe3)2]3 is difficult to
isolate due to the presence of solvent after purification, and a search through literature
results in no report utilizing this complex as a reagent, presumably due to this problem.
The preparation of the catalyst by the in situ formation of this precursor was also not
feasible due to the non-intuitive CrCl3(THF)3 to Li+-N(SiMe3)2 ratio of 1:1.5 used in its
synthesis. Therefore, a different approach was utilized in the attempt to prepare these
chromium alkoxy derivatives.
The alternate synthetic route involved the synthesis of the CrPh3(THF)3 precursor
using CrCl3(THF)3 and PhMgBr.55 The disadvantage to this route is the difficulty in
96
removing the MgBrCl produced, as the product and this salt are readibly soluble in
common organic solvents. An unfortunate consequence of the inability to remove the
salt is the formation of the Cr(salen)Br complex (1-3), which may occur via the
exchange of the alkoxy group in Cr(salen)(OR) and the bromine in MgBrCl to form
Mg(OR)Cl (eq. 4.1).58
(4.1)
This reaction pathway is plausible due to the favored formation of the more
thermodynamically stable polymeric Mg(OR)Cl species. Although not the desired
product, these chromium complexes serve as effective catalysts for the copolymerization
process as will be described shortly. However, the use of a larger, more sterically
encumbering group in the form of ROH, such as 2,4,6-trimethylphenol, presumably
results in the desired phenoxy initiator, Cr(salen)(OPh), 4.
The solid state characterization of two of these derivatives was obtained by
growing large dark red crystals via the slow diffusion of pentane into a THF or CH3CN
solution of the complex at -20˚C over a period of several weeks for X-ray analysis. In
this manner, structures of the THF (2.THF) and CH3CN (2.CH3CN) adducts of 2 were
obtained. Crystallographic data, and selected bond distances and angles for both
complexes are tabulated in Table 4.1 and Table 4.2, respectively. Thermal ellipsoid
representations of complexes 2.THF and 2.CH3CN showing 50% probability is depicted
Cr(salen)(OR) + MgBrCl Cr(salen)Br + Mg(OR)Clpolymeric
97
Table 4.1. Crystallographic data and data collection parameters for 2.THF, 2.CH3CN, 2. 2OPBu3 , 7a, and 8.
2.THF 2.CH3CN 2.2OPBu3 7a 8
Cryst syst monoclinic monoclinic monoclinic monoclinic triclinic
space group P2(1)/c P2(1)/c P2(1)/c P2(1)/n P1
V, Å3 4978(4) 4578(3) 6493(2) 10577(4) 2236.3(14)
Z 4 6 6 8 2
a, Å 16.386(8) 15.034(5) 16.571(4) 22.370(5)(2) 12.425(5)
b, Å 26.178(12) 17.377(6) 16.999(4) 20.764(5) 14.183(5)
c, Å 11.722(5) 17.692(6) 23.081(5) 23.028(6) 14.481(5)
α, deg — — — — 107.537(5)
β, deg 98.123(9) 97.890(6) 93.053(5) 98.579(5) 91.162(5)
γ, deg — — — — 111.668(5)
T, K 110 110 110 110 110 d(calc), g/cm3 1.280 1.271 1.175 1.325 1.349
Abs coeff, mm-1 1.082 1.166 0.885 0.319 0.582
R,a % [I > 2σ (I)] 8.92 10.95 7.20 7.91 8.17
Rw,a % 13.26 14.85 10.99 17.63 9.58 a R = Σ || Fo | – | Fc || / ΣFo and RwF = {[Σw(Fo – Fc)2] / ΣwFo
2}½
98
Table 4.2. Selected bond distances (Å) and angles for compounds 2.THF, 2.CH3CN, 2.2OPBu3, 7a, and 8.a
Complex 2.THF Cr(1)-N(1) 2.006(5) Cr(1)-O(2) 1.898(4) N(1)-C(2) 1.284(18) Cr(1)-N(2) 2.019(5) Cr(1)-Br(1) 2.4320(16) N(2)-C(18) 1.286(8) Cr(1)-O(1) 1.927(4) Cr(1)-O(3) 2.117(5) N(1)-Cr(1)-O(2) 173.2(2) N(2)-Cr(1)-O(3) 87.1(2) N(2)-Cr(1)-O(1) 172.4(2) N(1)-Cr(1)-O(1) 91.3(2) N(1)-Cr(1)-Br(1) 91.31(16) N(2)-Cr(1)-O(2) 91.7(2) N(2)-Cr(1)-Br(1) 88.59(16) N(1)-Cr(1)-N(2) 82.4(2) N(1)-Cr(1)-O(3) 88.5(2) Br(1)-Cr(1)-O(3) 175.65(13)
Complex 2.CH3CN Cr(1)-N(1) 2.004(6) Cr(1)-O(2) 1.924(5) N(1)-C(2) 1.313(10) Cr(1)-N(2) 2.015(7) Cr(1)-Br(1) 2.4191(18) N(2)-C(18) 1.305(10) Cr(1)-O(1) 1.913(5) Cr(1)-O(3) 2.100(7) N(1)-Cr(1)-O(2) 173.3(2) N(2)-Cr(1)-O(3) 85.3(3) N(2)-Cr(1)-O(1) 172.1(2) N(1)-Cr(1)-O(1) 91.9(2) N(1)-Cr(1)-Br(1) 90.92(18) N(2)-Cr(1)-O(2) 92.2(2) N(2)-Cr(1)-Br(1) 90.18(18) N(1)-Cr(1)-N(2) 81.7(3) N(1)-Cr(1)-O(3) 85.5(2) Br(1)-Cr(1)-O(3) 174.62(18)
99
Table 4.2 (Continued).
Complex 2.2OPBu3
Cr(1)-N(1) 2.004(4) Cr(1)-O(2) 1.925(3) N(1)-C(2) 1.305(6) Cr(1)-N(2) 2.008(4) Cr(1)-O(3) 2.005(3) N(2)-C(18) 1.309(6) Cr(1)-O(1) 1.910(3) Cr(1)-O(4) 2.003(3) N(1)-Cr(1)-O(2) 174.46(16) N(2)-Cr(1)-O(4) 92.21(15) N(2)-Cr(1)-O(1) 173.73(16) N(1)-Cr(1)-O(1) 92.43(15) N(1)-Cr(1)-O(3) 88.70(15) N(2)-Cr(1)-O(2) 91.74(15) N(2)-Cr(1)-O(3) 87.31(15) N(1)-Cr(1)-N(2) 82.86(16) N(1)-Cr(1)-O(4) 85.09(15) O(3)-Cr(1)-O(4) 173.78(15)
Complex 7a Cr(1A)-O(1A) 1.916(7) Cr(1A)-N(3A) 2.082(8) Cr(1A)-N(2A) 2.115(9) Cr(1A)-N(1A) 2.113(10) Cr(1A)-O(2A) 1.948(6) Cr(1A)-Cl(1A) 2.314(3) O(1A)-Cr(1A)-O(2A) 87.9(3) O(2A)-Cr(1A)-N(1A) 91.3(3) O(2A)-Cr(1A)-N(2A) 90.9(3) O(2A)-Cr(1A)-N(3A) 87.3(3) O(1A)-Cr(1A)-N(2A) 91.1(3) O(1A)-Cr(1A)-N(3A) 88.9(3) O(1A)-Cr(1A)-N(1A) 178.9(3) N(2A)-Cr(1A)-N(3A) 178.2(3) N(1A)-Cr(1A)-N(2A) 89.7(3) N(1A)-Cr(1A)-N(3A) 90.4(3) O(2A)-Cr(1A)-Cl(1A) 177.6(2) O(1A)-Cr(1A)-Cl(1A) 94.5(2) N(1A)-Cr(1A)-Cl(1A) 86.3(2) N(2A)-Cr(1A)-Cl(1A) 88.9(2) N(3A)-Cr(1A)-Cl(1A) 92.9(3)
100
Table 4.2 (Continued).
Complex 8 Cr(1)-O(1) 1.921(2) Cr(1)-Cl(1) 2.002(2) Cr(1)-N(2) 2.089(3) Cr(1)-N(1) 2.106(3) Cr(1)-O(2) 1.938(2) Cr(1)-Cl(1A) 1.999(3) O(1)-Cr(1)-O(2) 176.73(10) Cl(1)-Cr(1)-N(1) 167.87(11) O(1)-Cr(1)-N(1) 87.96(11) Cl(1)-Cr(1)-N(2) 90.85(11) O(1)-Cr(1)-N(2) 90.85(11) Cl(1)-Cr(1)-O(1) 85.52(10) Cl(1A)-Cr(1)-N(2) 170.45(11) Cl(1)-Cr(1)-O(2) 97.15(10) Cl(1A)-Cr(1)-Cl(1) 79.74(11) a Estimated standard deviations are shown in parenthesis.
101
in Figures 4.3 and 4.4, respectively. The chromium metal center in both complexes
exhibits octahedral geometry and lies perfectly within the plane formed by the N(1),
N(2), O(1), and O(2) atoms. Such planarity is similarly observed in aluminum and
chromium porphyrin complexes where the metal is pulled toward the plane upon
coordination of a Lewis base to the axial open site. The C(1)-Br(1) bond distance vary
slightly in the two complexes, with values of 2.4319(16) and 2.4190(18) Ǻ for
complexes 2.THF and 2.CH3CN, respectively. Another dissimilarity between the
complexes involves the bond length associated with the Schiff base (N=C) functionality,
with 2.THF having an average value (i.e., 1.286 Å) that is 0.026 Å shorter than that
found in 2.CH3CN. The Cr(1)-O(1), Cr(1)-O(2), Cr(1)-N(1), and Cr(1)-N(2) were also
found to be slightly longer in 2.CH3CN than in 2.THF.
Several attempts to obtain crystals with the relevant variety of phosphines (i.e.,
PCy3, PPh3, and PTA) bound to the chromium metal center were unsuccessful.
However, using the very air-sensitive PBu3 did prove effective, and although the oxide
was formed in the process, a suitable crystal was obtained of the bound O=PBu3 species,
2.2OPBu3. Dark, red crystals of 2.2OPBu3 were used to obtain a solid state structure.
Crystallographic data, and selected bond distances and angles of 2.2OPBu3 are tabulated
in Table 4.1 and Table 4.2, respectively. A thermal ellipsoid representation showing
50% probability is shown in Figure 4.5. The ease in displacing bromine by an excess of
a neutral ligand, such as O=PBu3, is clearly shown in the solid state, as the free Br- anion
is located in close proximity to the metal center on one face of the salen ligand. The
102
Figure 4.3. Thermal ellipsoid representation of Cr(salen)(Br)(THF), 2.THF, showing 50% probability.
103
Figure 4.4. Thermal ellipsoid representation of Cr(salen)(Br)(CH3CN), 2.CH3CN, showing 50% probability.
104
Figure 4.5. Thermal ellipsoid representation of [Cr(salen)(OPBu3)2]+[Br]-, 2.2OPBu3, showing 50% probability.
105
chromium metal center adopts a slightly distorted octahedral geometry with a N(1)-
Cr(1)-O(2) and O(1)-Cr(1)-N(2) bond angle of 174.46(16) and 173.73(16)˚, respectively.
The O(3)-Cr(1)-O(4) angle is nearly linear with a value of 173.78(15)˚. The Cr(1)-O(3)
and C(1)-O(4) bond distances were found to be 2.005(3) and 2.003(3) Å, respectively.
All other distances, including those pertaining to the N=C functionality are nearly
identical to that found in 2.THF.
Complexes 1-4 have been found to be effective catalysts in the copolymerization
of CO2 and epoxides with the aid of a phosphine cocatalyst. Catalytic activities
corresponding to these catalysts under varying conditions and with the use of different
phosphines are tabulated in Table 4.3.
Table 4.3. Activities associated with the use of catalysts 1-4 along with one equivalent of cocatalysta. Entry Catalyst Co-
catalyst Time (hr)
Polymer Yield (g)
TON (g poly. g Cr-1)b
TOF (g poly . g Cr-1 . hr-1)c
1 1d PCy3 12 20.85 3061 (1310) 255 (109)2 1 P(p-toly)3 12 18.90 2775 (1187) 231 (99)3 1 PPh3 12 8.98 1318(564) 110 (47)4 1 PTA 12 2.90 425 (182) 36 (15)5 1e PCy3 24 22.90 5055 (2158) 210 (90)6 1e PPh3 24 13.34 2944 (1257) 123 (52)7 2e PCy3 24 11.15 119 (47) 119 (47)8 3e PCy3 24 Trace ----------- -----------9 4e PCy3 24 15.09 3935 (1440) 164 (60)
a All copolymerizations were carried out at 80˚C under 800 Psi CO2 pressure using a 75 mg catalyst loading. b Values in parenthesis are in units of moles CHO consumed . mol Cr-1. c Values in parenthesis are in units of moles CHO consumed . mol Cr-1 . hr-1. d MW and Mn of the resulting polymer was found to be 6692 and 8397, respectively, translating into a PDI of 1.25. e A lower catalyst loading of 50 mg was used and the reaction carried out for 24 hr.
106
The use of very donating phosphines such as PTA resulted in low activities
which was contrary to what was expected. A possible explanation for the low activity
may be the low solubility of PTA in the CHO/liquid CO2 medium. Alternatively, the
phosphine may be interacting with the epoxide, in much the same manner PBu3 interacts
with epoxides and aziridines to ring open these substrates.59 Using other good electron
donors that are presumably unreactive toward epoxides such as PCy3 resulted in an
increase in activity by more than a factor of ten in only 12 hours when compared to the
N-MeIm system.23 The utilization of less electron donating phosphines such as PPh3 or
P(p-toly)3 resulted in a slight drop in activity as well as in the percent CO2 incorporation.
Lowering the catalyst loading and carrying the reaction for 24 hrs (entry 5 and 6) results
in an increase in TON, but decreases the TOF due to the longer reaction period. Catalyst
bearing the phenyl backbone, 2 and 3, are found to be less active and is presumably due
to a less electron rich metal center, as most of the electron density is likely contained
within the pi system of the ligand framework (entry 7 and 8). This is especially true for 3
as only trace amounts of copolymer was produced with the major product being
cyclohexene carbonate. Such changes in activity create the potential to maximize
polymer formation by tuning the ligand framework.
Induction periods and maximum rates associated with the use of 1 were obtained
by the monitoring of the v(CO2) stretch of the polymer peak in situ using an ASI 1000
ReactIR probe fitted with a modified stainless steel Parr reactor. A typical 3-D reaction
profile using PCy3 as the cocatalyst is provided in Figure 4.6. The peak traces
107
Figure 4.6. Three-dimensional plot of copolymer growth at 1750 cm-1 using Cr(salen)Br, 1, with one equivalent of PCy3.
108
corresponding to the growing polymer chain at 1750 cm-1 using different phosphines is
presented in Figure 4.7. The maximum rate obtained using the strongly donating PCy3
was found to be 2.3 x 10-4 Abs/min, and as expected, is the largest when compared to the
use of other phosphines (Table 4.4).
Table 4.4. Maximum rates and induction periods in the copolymerization of CO2 and epoxides using 1 as the catalyst. Entry Catalyst Co-catalyst Induction Period (min) Max Rate (10-4) (abs/min)
1 1 PCy3 None 2.3 2 1 P(p-toly)3 None 2.0 3 1 PPh3 None 0.9 5 1 PTA None 0.2 6 2 PCy3 None 0.8 7 4 PCy3 30 0.9
More importantly, however, is the lack of an induction period, indicating a deviation
from the Jacobsen initiation process, and presumably points toward a first order
initiation. In addition, no cyclic carbonate (appears at 1817 cm-1 for the trans species)
was ever detected using the strongly donating cocatalysts. Using 4 as the catalyst, the
reaction profile reveals an induction period of 30 minutes, and is consistent with either a
slow CO2 insertion into the Cr-OPh bond (insertion into M-OPh bonds are orders of
magnitude slower than in typical M-OR bonds) or a slow ring opening of the epoxide by
the OPh functionality.60
The copolymerization of CO2 and PO was carried out using 1 as the catalyst. At
40˚C under 610 psi CO2 pressure using 50 mg of 1 with one equivalent of PCy3 as the
cocatalyst, resulted in predominantly propylene carbonate with minor amounts of
copolymer after 24 hr. Surprisingly, carrying out the reaction at room temperature under
109
-0.010
0.090
0.190
0.290
0.390
0.490
0.590
0.690
0.790
0.890
0.990
0 100 200 300 400 500 600 700 800
Time (min)
Abs
orba
nce
PCy3
P(p-tol)3
PPh3
PTA
Figure 4.7. Trace of 1750 cm-1 copolymer growth using several different phosphines with Cr(salen)Br, 1, as the catalyst.
110
the same conditions resulted in all propylene carbonate production. The high amounts
of cyclic carbonate may be explained by a highly active system in which the very
electron rich metal center creates a more nucleophilic -OP group, which can back-bite
through the mechanism proposed by Kuran (see Chapter I), and release the cyclic
carbonate product.19b It is surprising, however, that the production of polycarbonate,
although low, occurs at higher temperatures and not at room temperature. Such a trend
is typically not observed with transition metal coupling reactions of CO2 and epoxides
due to the higher activation barrier for cyclic carbonate formation.23
Two terpolymerization reactions were carried out using TMSO and CHO as well as
TMSO and PO as monomers. In the former, using a 1:1 TMSO to CHO ratio by volume
(30.4% TMSO by mole) under 800 psi CO2 pressure for 24 hr using 50 mg of 1 with one
equivalent of PCy3 as the cocatalyst, a TON of 4893 g polymer . g Cr-1 was obtained and
translates in a TOF of 204 g polymer . g Cr-1 . hr-1. Only trace amounts of cyclic
carbonate was observed as indicated by IR spectroscopy of the reaction mixture. The
percent CO2 incorporation within the polymer was not determined due to the -Si(OCH3)3
resonance falling in the same range as the polyether signals in the 1H NMR spectrum.
The 1H NMR spectrum does, however, present one interesting feature . In the
polycarbonate range (~4.6 ppm), one broad signal is clearly visible consisting of a
shaper, well defined peak with a shoulder. Presumably, two signals are present
corresponding to the carbonate linkages of the CHO and TMSO linkages, respectively.
The point of coalescence may be due to the alternating TMSO/CHO carbonate units. In
the terpolymerization of CO2, PO, and TMSO (62.3% PO by mole), using the same
111
reaction conditions, the resulting reaction mixture was found to consist of a large amount
of propylene carbonate and is supported by the 1H and 13C NMR spectrum of the
polymer. In the 1H NMR, however, the two broad signals at 4.86 and 4.06 ppm
correspond to the propylene carbonate linkages, while the resonance at 3.64 ppm
belongs to the propylene ether linkages (Figure 4.8). The broad signal at 4.62 is most
likely due to the TMSO carbonate linkages. An important feature of the polymer is the
ability to crosslink with propylene carbonate being absorbed within the network, giving
a soft and pliable polymeric material.
The planar geometry and trans nature of the nucleophile relative to the open site
created by the salen ligand framework is an essential feature for an active catalytic
system. This is supported by the synthesis of an analogous chromium complex bearing
two salicylaldimine units, creating the bis complex, 6 (Scheme 4.1).56 The synthesis of
6 is achieved by the reaction between CrCl3(THF)3 and two equivalents of the
salicylaldimine lithium salt. Although not isolated, 6 presumably adopts a square
pyramidal geometry, similar to Cr(salen)Cl complexes. However, the addition of a
Lewis base, such as CH3CN, results in the formation of the octahedral complex 7, where
the labile CH3CN molecule coordinates in a manner cis to the nucleophile (i.e.,
chloride). In addition, coordination is also accompanied by a color change of the
solution from brown to green. Such coordination is illustrated in the solid state structure
of 7a. Crystallographic data, and selected bond distances and angles are presented in
Table 4.1 and Table 4.2, respectively. A thermal ellipsoid representation showing 50%
112
Figure 4.8. 1H NMR of CO2/PO/TMSO terpolymer using Cr(salen)Br, 1, as the catalyst with one equivalent of PCy3.
5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6
4.85
4.70
4.62
4.43
4.06
3.89
3.64
OO
O
CH3
Propylene Carbonate (PC)
PC PC
PC
ab
c
d
OO*
O
O O
O
O
Si(OCH3)3
x y zab c
d
113
Scheme 4.1
N
Ph
HO
1. n-BuLi, -780C, THF2. CrCl3(THF)3, -780C, THF Cr
N
O
O
NCl
2
6a,b
LCr
N
O
L
NCl
O
7a,b
a. R1=Ph, R2=R3=Hb. R1=R2=tert-Bu, R3=Hc. R1=H, R3=CH(CH)2CH=R4
No sterically demandinggroup in R1 position(i.e., c)
1. n-BuLi, -780C, THF2. CrCl3(THF)3, -780C, THF
CrN
N
Cl
ClO
O
CrN
NO
O
8
114
probability is shown in Figure 4.9. The Cr(1)-N(3A) bond distance is found to have a
value of 2.082(8) Å, and is nearly identical to that found in 7b. More importantly,
however, is the cis orientation adopted upon exposure of 6 to a Lewis base (e.g.
epoxide). The copolymerization, with 6 as the catalysts, was carried out using 20 mL of
CHO and 800 psi CO2 pressure at 80 ˚C for a 24 hr reaction period, resulting in a far
inferior catalytic system when compared to 1-4. Copolymer was produced in low yield
and its composition consisted of 50% ether linkages, indicating subsequent epoxide ring
opening steps. Furthermore, substantial amounts of cyclohexene carbonate was also
produced. Upon carrying out the same copolymerization in the presence of 2.25
equivalents of N-MeIm, a further reduction in polymer yield resulted with the polymer
being composed of approximately 50% ether linkages. The coordination of this stronger
Lewis base to the metal center can be viewed in Figure 4.10. The almost complete loss
in activity associated with these types of catalysts clearly illustrates the need for a planar
ligand framework. Perhaps the use of a more electron donating salicylaldimine can
result in a more active catalytic system, but due to the cis nature of the open site relative
to the binding site of the epoxide, consecutive epoxide ring opening processes may
occur, leading to high ether linkages within the polymer. The attempt to synthesize a
series of these salicylaldimine complexes bearing less sterically encumbering groups on
the salicylaldimine was unsuccessful, and resulted in the formation of chromium dimers.
For example, using the salicylaldimine with substitution facing away from the
115
Figure 4.9. Thermal ellipsoid representation of Cr(1/2Sal)2(CH3CN)(Cl), 7a, showing 50% probability.
116
Figure 4.10. Ball and stick representation of Cr(1/2Sal)2(Cl)(N-MeIm).
117
hydroxyl aromatic ring (e.g., salicylaldimine c), resulted in the formation of the dimer, 8
(Scheme 4.1). The solid state structure of 8 was obtained by growing suitable crystals of
this compound by the slow diffusion of pentane into an acetonitrile solution of 8 at -20
˚C. Crystallographic data, and selected bond distances and angles for this species are
found in Table 4.1 and Table 4.2, respectively. A thermal ellipsoid representation
showing 50% probability is presented in Figure 4.11. As shown, the dimer is bridged by
two chloride atoms, and the two salicylaldimine units are oriented away from each other
to facilitate the formation of the complex. The C(1)-Cl(1) and Cr(2)-Cl(2) bond
distances were found to have a value of 2.002(2) and 1.999(3) Å, and are approximately
0.30 Å shorter than that found in 7. Attempts to grow crystals of the epoxide-bound
analogue to 7 using a variety of epoxides such as α-pinene oxide, norbornene oxide, and
limonene oxide, all of which are less prone to being ring-opened, were unsuccessful.
CONCLUDING REMARKS
The synthesis of Cr(salen)X (X = Br, OPh) catalysts for the copolymerization of
CO2 and epoxides was successful employing the CrPh3(THF)3 precursor. Although the
brominated species was not the initial target complex, they were found to be effective
catalysts for the copolymerization of CO2 and CHO. Characterization of several of these
derivatives was achieved by X-ray crystallography. The chromium metal center in the
solid state adopts an octahedral geometry in the presence of bound solvent or phosphine
118
Figure 4.11. Thermal ellipsoid representation of [Cr(1/2Sal)2(Cl)]2, 8, showing 50% probability.
119
oxide. An important observation involves the facile dissociation of the bromide ion in
the presence of phosphine, and supports the lack of an induction period in the initiation
step. Potentially, initiation can be envisioned to take place via a first order route where
the phosphine effectively activates the nucleophile (i.e., Br-) to ring open the epoxide
(Figure 4.12).
Cr
BrO
PR3
Figure 4.12. Initiation step involving Cr(salen)X catalysts, 1-4, with PR3 activation.
Productivity as a function of PR3 was found to increase using the more electron donating
phosphines: PCy3>P(p-tol)3>PPh3. However, using the most electron donating PTA
species (or other similar phosphines) results in a far inferior system due to, a
presumably, less soluble nature of PTA in CHO/liquid CO2 or the potential interaction
with epoxide. TON's and TOF's were found to be as high as 2158 mol CHO consumed .
mol Cr-1 and 90 mol CHO consumed . mol Cr-1 . hr-1, respectively, and are much higher
than those previously reported for the Cr(salen)Cl/N-MeIm system.23
The importance of the trigonal pyramidal geometry of the catalyst was illustrated by
the synthesis of other Schiff base analogues (i.e., 7a). These systems are far less active
and only afford polyether due to the consecutive ring-opening of the epoxide as a result
120
of the cis coordination of the epoxide relative to the nucleophile. Additionally, the
synthesis of other derivative not having sterically encumbering groups next to the
oxygen on the phenoxy ring affords bimetallic derivatives.
121
CHAPTER V
SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF IRON(III)
SALEN COMPLEXES POSSESSING ANIONIC OXYGEN DONOR LIGANDS*
INTRODUCTION
Optimization of catalytic activities for a given process is typically achieved through
the methodical tailoring of the metal’s ligand environment. Therefore, ligand
frameworks such as the Schiff base containing salen ligand, that can be sterically and
electronically modified with ease, are very attractive.61 The use of the salen ligand
framework in catalytic reactions has been receiving increasing interest due to the
aforementioned advantage and its success in many newly discovered processes. Most
notable is the asymmetric ring opening (ARO) of epoxides by a Cr(salen)Cl catalyst
which was developed by Jacobsen and workers in the mid-1990's.24 Additionally, the
oxidation of alkenes via M(salen)Cl (M = Mn, Cr) catalysts in the presence of an oxygen
donor also spurred intense research in the area of Schiff base chemistry.62 A very
important reaction in organic synthesis which involves the use of predominantly
chromium based salen complexes is the Diels-Alder reaction. Indeed, there are
numerous reports where these catalysts have been employed as part of a long synthetic
strategy to afford complex natural products.63
_______________ * Reproduced in part with permission from Darensbourg, D. J.; J. C.; Ortiz, C. G.; Billodeaux, D. R. Inorg. Chim. Acta. In Press.
122
One of the most widely used and applicable synthetic methodologies is the
carbon-carbon coupling reaction, which is dominated by palladium based catalysts.64
Although unprecedented results have been obtained using this metal through the years,
the high cost of many of these catalysts is an immense drawback. An alternative and
highly under explored option is the use of iron catalysts which possess many advantages
over traditional catalyst due to iron’s copious, non-toxic, and inexpensive nature. The
use of Fe(salen)Cl as a pre-catalyst in the cross-coupling of aryl chlorides and Grignard
alkyls has been recently investigated and found to be highly effective.65 Such report
opens a new avenue for the utilization of iron salen complexes in organometallic
catalysis.
In this context, few investigations incorporating iron as the metal center in the
copolymerization of CO2 and epoxides to afford polycarbonate have been conducted.
Due to the success associated with the Cr(salen)Cl catalyst for this purpose, the search
for new catalysts bearing the salen ligand framework with a variety of metals is of
interest.23 Herein, we wish to report the synthesis of a novel Fe(salen)(OPh), 1,
complex, incorporating 2,6-diphenylphenoxy moiety in the axial site (Figure 5.1). The
synthetic strategy for the preparation of these types of complexes is discussed as well the
solid state characterization of 1. The Fe(salen)(acac), 2, complex has also been prepared
through the use of a previously reported synthetic route (Figure 5.1).66 The
123
N N
O O
Fe
t-Bu
t-Bu t-Bu
t-Bu
O
PhPh
N N
O O
Fe
t-Bu
t-But-Bu
t-Bu
O
O
= acacO
O
1 2
Figure 5.1. Fe(salen)X complexes incorporating monodentate and bidentate anionic ligands.
124
coordination mode of a bidentate ligand such as acetylacetonate induces dramatic
changes in the geometry at the metal center.
In addition, the solid state characterization of the µ-oxo dimer, 3, is presented.
Such species are of importance due to the many bioinorganic processes involving
dioxygen activation.67 For example, methane monooxygenase effectively cleaves the O2
bond to produce one molecule of both water and methanol. Although it is not the
purpose of this manuscript to fully compare the oxo species to relevant bioinorganic
models, many important physical attributes such as selected bond distances and angles
are provided. Additionally, µ-[Fe(salen)]2O complexes of this type have also been used
in the catalytic olefin cyclopropanation reaction to afford many useful organic
substrates.68
EXPERIMENTAL
Methods and Materials
Unless otherwise indicated, all reactions were carried out under an inert argon
atmosphere using standard Schlenk and drybox techniques. Prior to their use, all
solvents were distilled using standard techniques. The synthetic precursors, FeCl3,
Fe(acac)3, 2,6-diphenylphenol, and 1,2-ethyldiamine were purchased from Aldrich
Chemical Co. 2,6-Diphenylphenol was purified by sublimination prior to its use. The
preparations of Fe[N(Si(CH3)3)2]358 and 3,5-di-tert-butyl-2-hydroxybenzaldehyde33 were
accomplished by the literature procedures. The synthesis of N,N'-bis(3,5-di-tert-
butylsalicylidene)-1,2-ethyldiimine (salen) 23a was accomplished by the typical protocol
125
of refluxing 1,2-ethyldiamine and 3,5-di-tert-butyl-2-hydroxybenzaldehyde in methanol
over a period of 5 hr in the presence of molecular sieves.
After each CO2/epoxide copolymerization experiment, the resulting reaction
mixture was analyzed by IR spectroscopy using a Mattson 6021 FTIR spectrometer with
DTGS and MCT detectors. X-ray data were recorded using a Bruker Smart 1000 CCD
diffractometer.
Synthesis of Fe(salen)(OPh) (1)
To a 100 mL Schlenk flask was added Fe[N(Si(CH3)3)2]3 (0.150 g, 0.28 mmol)
which was dissolved in approximately 15 mL of toluene. To the resulting green solution
was added the H2salen ligand (0.138 g, 0.28 mmol) in 15 mL of toluene via cannula
technique, and the dark solution was stirred for approximately 2 hr. Freshly sublimed
2,6-diphenylphenol (0.069 g, 0.28 mmol), in 10 mL of toluene, was cannulated into the
reaction solution to afford a deep red solution which was stirred overnight.
Subsequently, the solvent was removed under vacuum, and the remaining solid was
dried. Yield: 92.8%. The complex was characterized by X-ray crystallography via the
use of dark, plate-like crystals formed by the slow diffusion of pentane in a methylene
chloride solution of 1 at -20ºC.
Synthesis of Fe(Salen)(acac) (2)66
The synthetic methodology employed in the synthesis of this derivative was
identical to that reported by Cheng and coworkers. To a 50 mL Schlenk flask equipped
with a condenser was added Fe(acac)3 (0.300 g, 0.85 mmol) and the H2salen ligand
(0.415 g, 0.85 mmol) in approximately 30 mL of acetonitrile. The resulting red solution
126
was refluxed for 2 hr, causing the formation of a dark purple solution. The solution was
filtered and the solvent was removed under vacuum. Complex 2 was characterized by
X-ray crystallography using purple crystals formed by the diffusion of pentane into a
toluene solution of 2 at -20ºC.
Copolymerization of CO2 and Epoxides
A typical reaction was carried out using the following protocol. A 35 mL glass vial
with a septum was charged with 1 (50 mg, 0.063 mmol) followed by the addition of 20
mL of cyclohexene oxide. To this solution was added via microliter syringe N-MeIm
(11.7 mg, 0.142 mmol, 11.3 µL). The solution was then introduced into the stainless
steel autoclave via an injection port followed by pressurizing the reactor to
approximately 550 psi CO2 pressure at room temperature. The temperature was raised to
80ºC, at which time the CO2 pressure increased to 800 psi. The reaction was carried out
for 24 hr, after which the heat was turned off and the reactor was allowed to cool to
room temperature. After venting the excess CO2, the reactor was cleaned by dissolving
any polymer with methylene chloride. An infrared spectrum of the reaction mixture was
immediately taken in CH2Cl2 to determine the extent of polycarbonate and cyclohexene
carbonate formation.
RESULTS AND DISCUSSION
The preparation of complexes 1-2 was achieved via two independent synthetic
routes. Complex 1 was synthesized using the Fe[N(Si(CH3)3)2]3 precursor with one
equivalent of H2salen and the corresponding phenol (Scheme 5.1). Immediately, after
127
N N
O O
Fe
t-Bu
t-Bu t-Bu
t-Bu
O
PhPh
1
Fe[N(Si(CH3)3)2]3 +
N N
OH HOt-Bu
t-Bu t-Bu
t-Bu 2,6-DiphenylphenolToluene, r.t., overnight
Scheme 5.1
128
the addition of the H2salen ligand to the Fe[N(Si(CH3)3)2]3 green precursor, a deep red
solution was observed.58 Characterization of 1 was achieved by growing dark, plate-like
crystals via the slow introduction of pentane into a toluene solution of 1 at -20ºC. An X-
ray analysis of the bulk crystals resulted in the solid state characterization of 1.
Crystallographic data, and selected bond distances and angles are tabulated in Table 5.1
and Table 5.2, respectively. A thermal ellipsoid representation of 1 showing 50%
probability is provided in Figure 5.2. The iron center is found to adopt a distorted square
pyramidal geometry with the N(1)-Fe(1)-O(2) and N(2)-Fe(1)-O(1) bond angles having
values of 131.3(3) and 159.1(3)º, respectively. An expanded view of the metal center
with its immediate coordination sphere is presented in the inset in Figure 5.2. Such
orientation is not surprising and is also observed in other M(salen) complexes
incorporating the ethyl backbone fragment within the ligand framework.69 The Fe(1)-
O(1) and Fe(1)-O(2) bond distances were found to be 1.894(7) and 1.887(6) Å and are
nearly identical to the Fe(1)-O(3) bond distance (i.e., 1.876(8) Å) pertaining to the
phenoxy axial ligand. The N(1)-C(2) and N(1)-C(18) bond distance were found to differ
significantly from each other with values of 1.301(12) and 1.249(12) Å, respectively.
Such differences in the N=C bond distance within the same salen framework is not
typical.
The acetylacetonate derivative, 2, was successfully prepared thermally by reacting
one equivalent of H2salen with Fe(acac)3 in acetonitrile under refluxing conditions
(Scheme 5.2). This protocol has been previously used in the preparation of chiral iron
complexes bearing binaphthyl Schiff base analogues.67 The procedure leads
129
Table 5.1. Crystallographic data and data collection parameters for complexes 1, 2, and 3.
1 2 3
Cryst syst monoclinic monoclinic monoclinic
space group P2(1)/n C2/c C2/c
V, Å3 4704(2) 7475(3) 6567(7)
Z 4 8 6
a, Å 16.130(4) 24.801(5) 24.546(14)
b, Å 16.123(5) 10.637(2) 16.707(10)
c, Å 19.555(6) 28.336(6) 17.075(10)
α, deg — — —
β, deg 112.320(6) 90.258(4) 110.315(10)
γ, deg — — —
T, K 110 110 110
d(calc), g/cm3 1.235 1.197 1.227
Abs coeff, mm-1 0.477 0.444 0.498 R,a % [I > 2σ (I)] 9.73 6.64 5.37
Rw,a % 27.07 10.25 5.85 a R = Σ || Fo | – | Fc || / ΣFo and RwF = {[Σw(Fo – Fc)2] / ΣwFo
2}½
130
Table 5.2. Selected bond distances (Å) and angles for complexes 1, 2, and 3.a
Complex 1 Fe(1)-N(1) 2.094(9) Fe(1)-O(2) 1.887(6) Fe(1)-O(3) 1.876(8) Fe(1)-N(2) 2.091(9) N(1)-C(2) 1.301(12) N(1)-C(1) 1.448(13) Fe(1)-O(1) 1.894(7) N(2)-C(18) 1.249(12) N(2)-C(17) 1.478(13) O(1)-Fe(1)-N(2) 159.1(3) N(2)-Fe(1)-O(1) 159.1(3) O(2)-Fe(1)-N(1) 131.3(3) N(2)-Fe(1)-O(2) 85.7(3) N(1)-Fe(1)-O(3) 110.9(3) N(1)-Fe(1)-N(2) 77.3(4) N(1)-Fe(1)-O(1) 86.8(3) O(1)-Fe(1)-O(2) 95.0(3) N(2)-Fe(1)-O(3) 92.9(3) O(1)-Fe(1)-O(3) 105.5(3)
Complex 2 Fe(1)-N(1) 2.154(4) Fe(1)-O(2) 1.934(3) Fe(1)-O(3) 2.060(3) Fe(1)-N(2) 2.124(4) N(1)-C(2) 1.288(6) Fe(1)-O(4) 2.006(3) Fe(1)-O(1) 1.898(3) N(2)-C(18) 1.287(6) N(1)-C(1) 1.471(6) N(2)-C(17) 1.461(6) O(1)-Fe(1)-N(2) 156.61(15) N(2)-Fe(1)-O(1) 156.61(15) O(2)-Fe(1)-N(1) 111.00(14) N(2)-Fe(1)-O(2) 82.30(14) N(1)-Fe(1)-O(3) 80.38(14) N(1)-Fe(1)-N(2) 75.38(15) N(1)-Fe(1)-O(1) 84.52(14) O(1)-Fe(1)-O(2) 94.12(13) N(2)-Fe(1)-O(3) 160.81(13) O(1)-Fe(1)-O(3) 102.53(14) O(4)-Fe(1)-N(2) 109.78(14) O(4)-Fe(1)-O(2) 85.88(13) O(4)-Fe(1)-N(1) 163.04(14) O(4)-Fe(1)-O(3) 83.84(14)
131
Table 5.2 (Continued).a
Complex 3
Fe(1)-N(1) 2.116(3) Fe(1)-O(2) 1.926(2) Fe(1)-O(3) 1.7653(10) Fe(1)-N(2) 2.100(3) N(1)-C(2) 1.267(4) N(1)-C(1) 1.453(4) Fe(1)-O(1) 1.917(2) N(2)-C(18) 1.282(4) N(2)-C(17) 1.469(4) O(1)-Fe(1)-N(2) 174.26(9) N(2)-Fe(1)-O(1) 134.26(9) O(2)-Fe(1)-N(1) 156.18(9) N(2)-Fe(1)-O(2) 86.30(9) N(1)-Fe(1)-O(3) 97.50(10) N(1)-Fe(1)-N(2) 76.67(9) N(1)-Fe(1)-O(1) 84.44(9) O(1)-Fe(1)-O(2) 96.10(9) N(2)-Fe(1)-O(3) 113.58(8) O(1)-Fe(1)-O(3) 109.92(7) Fe(1)-O(3)-Fe(1A) 171.63(17)
a Estimated standard deviations are shown in parenthesis.
132
Figure 5.2. Thermal ellipsoid representation of Fe(salen)(OPh) (1) showing 50% probability.
133
N N
O O
Fe
t-Bu
t-But-Bu
t-Bu
O
O
= acacO
O
2
Fe(acac)3 +
N N
OH HOt-Bu
t-Bu t-Bu
t-Bu
CH3CN, reflux, 2 hr
Scheme 5.2
134
to the production of the desired product in good yields (>80%). Allowing the slow
diffusion of pentane into a toluene solution of 2 resulted in bulk X-ray quality dark
crystals. Crystallographic data, and selected bond distances and angles are presented in
Table 5.1 and Table 5.2, respectively. A thermal ellipsoid representation of 2 showing
50% probability is given in Figure 5.3. As has been previously described in the
analogous complexes, the use of the bidentate acetylacetonate ligand demands the iron
center to adopt a distorted octahedral geometry (inset in Figure 5.3). For example, the
N(1)-Fe(1)-O(2) and N(2)-Fe(1)-O(1) bond angles are found to have values of
111.00(14) and 156.61(15)º, respectively. The large deviation from the typical square
pyramidal geometry associated with M(salen)Cl (M = Cr, Fe, Mn) complexes is clearly
evident by other bond angle data presented in Table 5.2. The Fe(1)-O(1) and Fe(1)-O(2)
bond distances are found to have values of 1.898(3) and 1.934(3) Å, respectively. Such
deviation from one another is not surprising due to the octahedral nature of the iron
center. As expected and observed in other Fe(salen)(acac) complexes, the Fe(1)-O(4)
bond distance is approximately 0.06 Å shorter than the Fe(1)-O(3) distance
corresponding to the acetato ligand.66 Unfortunately, using 1 as a catalyst in the
copolymerization of CO2 and cyclohexene oxide was unsuccessful. The addition of 2.5
equivalents of the Lewis base, N-MeIm, to 1, in cyclohexene oxide, also resulted in an
inactive system. Perhaps the use of electron deficient OPh groups as initiators are not
suitably nucleophilic for either the ring opening of epoxides or the CO2 insertion into the
Fe-OPh bond even in the presence of an auxiliary Lewis base. Additionally, using 2 also
135
Figure 5.3. Thermal ellipsoid representation of Fe(salen)(acac) (2) showing 50% probability.
136
resulted in no polycarbonate production, and yielded only low amounts of cyclohexene
carbonate with PCy3 as the cocatalyst.
An attempt to synthesize the iron amido derivative, Fe(salen)(N(Si(CH3)3)2), was
unsuccessful, and due to the highly unstable nature of this intermediate, the hydrolysis
product was readily formed as indicated by the formation of the µ-oxo dimer, 3. The
complex is air stable and forms perfect rectangular black crystals in large quantities. A
solid state structure of the complex was obtained by X-ray crystallography.
Crystallographic data, including selected bond distances and angles are tabulated in
Table 5.1 and Table 5.2, respectively. A thermal ellipsoid drawing showing 50%
probability is shown in Figure 5.4. Due to the sterically encumbering tert-butyl groups
on the ligand framework, the iron centers are stacked in a 100.9º rotation with respect to
one another to afford the most stable conformation. The Fe(1) atom is also found to lie
0.566 Å above the plane formed by the N(1), N(2), O(1), and O(2) atoms. Such
deviation is typical and observed in other [Fe(salen)]2O species.70 The two complexes,
bridged by the lone oxygen atom, O(3), form a nearly linear Fe(1)-O(3)-Fe(1A) angle
with a value of 171.63(17)º, similar to the other salen Fe complexes and porphyrin
derivatives such as [Fe(TTP)]2O (TTP = meso-tetrakis(p-tolyl)-porphyrinato) (i.e.,
178.2(3)º).71 The linear characteristic of the Fe-O-Fe unit is heavily dependent on the
aryl substituents as sterically encumbering groups aid in the formation of a linear angle
by imposing electronic and steric repulsions between the ligands while those possessing
less sterically encumbering groups cause a more bent framework (i.e., no substitution on
salen: Fe(1)-O(1)-Fe(2)=156.5(3)º).70 The Fe(1)-O(3) bond distance
137
Figure 5.4. Thermal ellipsoid representation of µ-[Fe(salen)]2O (3) showing 50% probability.
138
is approximately 0.11 Å shorter than that found in the phenoxy analogue, 1, while the
Fe(1)-N(2) bond distance was found to be slightly longer than those found in 1.
CONCLUDING REMARKS
Iron complexes, 1-2, bearing the Schiff base containing a salen ligand were
successfully synthesized using two synthetic approaches. The use of Fe[N(Si(CH3)3)2]3
as a precursor with one equivalent of both the H2salen and 2,6-diphenylphenol ligand
has been found to be an effective route for the preparation of 1, and is a feasible
synthetic route for the synthesis other iron complexes bearing an array of OR groups in
the axial position. Yields are excellent due to the ease in removing the HN(Si(CH3)3)2
byproduct under reduced pressure. Characterization of 1 was achieved by X-ray analysis
of small plate-like crystals. The primary purpose behind the preparation of 1 was to
determine its catalytic activity in the copolymerization of CO2 and epoxides.
Unfortunately, a completely inactive system was observed using cyclohexene oxide as
the epoxide, even in the presence of a Lewis base cocatalyst. Perhaps, derivatives
incorporating alkoxy groups or more electron rich phenoxides coordinated to the iron
center may serve as better nucleophiles for the CO2 or ring opening initiation step.
Adding bidentate ligands, such as acetylacetonate, has been found to cause dramatic
coordination changes. In 2, the iron adopts a very distorted octahedral geometry,
indicating a strong preference for the square pyramidal analogues, as has been observed
in many other M(salen)X complexes, where X represents an anionic monodentate
ligand.69 A lack of catalytic activity was also observed using 2 as the catalyst for the
139
aforementioned copolymerization process with the use of PCy3 as the cocatalyst.
Furthermore, the hydrolysis of two equivalents of Fe(salen)(N(Si(CH3)3)2) with a proton
source (e.g., water), yields the µ-oxo derivative, 3. Complex 3 was also characterized by
X-ray crystallography and found to be similar to other analogues incorporating sterically
encumbering groups on the salen framework. This air stable derivative may serve as an
active catalyst in the olefin cyclopropanation reaction due to the potential formation of a
more stable Fe(II) intermediate than those formed with related complexes.68
140
CHAPTER VI
METHYLATION REACTIONS OF GROUP 10 1,3,5-TRIAZA-7-
PHOSPHAADAMANTANE COMPLEXES USING CH3OSO2F AND SYNTHESIS
OF NOVEL PALLADIUM-NICKEL DACO TRIMERS
INTRODUCTION
At the active sites of many enzymes lie transition metal complexes which catalyze
important biochemical reactions. One of the most widely studied metalloenzymes is the
carbon monoxide dehydrogenase (CODH)/acetyl-coenzyme A synthase (ACS) which
reversibly reduces CO2 to CO, and subsequently couples the molecule with CH3 and
CoA to form Acetyl-CoA.72,73 The harboring of CO2 as an energy source in order to
produce biomass allows microorganisms such as Moorella thermoacetica to thrive using
this very primitive energy production process. The two primary metallocofactors in the
CODH and ACS units are the C and A cluster. The former is responsible for the
reversible reduction of CO2 while the latter’s function is to couple CO, CH3, and CoA (a
thiol, SR-) to form the final thioester product. The active site in the A cluster is
composed a [Fe4S4] unit bridged by a metal atom that is linked to a nickel complex
composed of a N2S2 framework which originates from cysteine (S) and glycine (N)
residues (Figure 6.1).
Figure 6.1. Active site in the A cluster of Acetyl CoA Synthase.
[Fe4S4] S(Cys) M
L
S(Cys)
S(Cys)Ni
N(Cys)
N(Gly)
141
The metal atom represented as M in Figure 6.1 has been a subject of much debate, with
researchers identifying it as copper, nickel, or zinc.73, 74 Regardless of its identity, a
neutral ligand, L, is coordinated to this metal center, and most likely represents a CO
molecule. The proposed mechanism by Lindahl in the formation of Acetyl-CoA is
represented in Scheme 6.1.73a In the first step, a CH3 group is donated by a cobalt
complex (i.e., methyl cobalamine, denoted as CH3-[Co] in Scheme 6.1), forming the
nickel alkyl species which subsequently inserts CO to form the nickel acyl complex.
Nucleophilic attack by CoA- followed by reductive elimination leads to the formation of
Acetyl-CoA.
Herein, we present synthetic strategies for the preparation of model bimetallic
complexes of the type [(N2S2)Ni]-[Pd(XR)(CH3)] (X=O, S). Such complexes would be
analogous to the bimetallic site in Figure 6.1. Although nickel is the primary choice,
palladium typically provides more stable complexes which may be isolated and
characterized by X-ray crystallography. The [(N2S2)Ni] complex chosen for the study is
the (BME-DACO)Ni75 and (BME-DACH)Ni76 species, as they are synthesized with
relative ease and the latter using commercially available reagents. Additionally, the two
sulfur atoms are suitable donors to stabilize a second metal center, and lack any type of
steric influences that may prohibit binding.
The methyl transfer and CO insertion pathway (in Scheme 6.1) is primarily
supported by model complexes developed by Holm,77 Norton,78 and others.79 For
example, Norton has previously synthesized a [Co]CH3 complex that effectively
142
Scheme 6.1
SR [Ni]
SR [Ni] CH3
CH3 [Co]
SR [Ni] C(O)CH3
CoA-
CH3 CoA
O
CO Insertion
(Cobalt Corronoid Protein)
143
transfers the covalently coordinated methyl group to a [Ni] complex to produce the
[Ni]CH3 species. Herein, in a collaborative effort with Dr. Paul Lindahl from Texas
A&M University, we wish to focus on the preparation of Group 10 water-soluble methyl
complexes that might model the methyl transfer feature of ACS. Hundreds of water-
solubilizing ligands have appeared through the years, with the most common based on
tertiary phosphines such as the meta-triply sulfonated triphenylphosphine derivative,
TPPTS.31 However, we wish to focus on non-salt containing phosphines such as the
aliphatic, heterocyclic 1,3,5-triaza-5-phosphaadamaantane (PTA) ligand, which has been
found to be a good donor due to electronic and steric influences.11 In this report, we
present the attempted methylation of M(PTA)4 (M = Ni (1), Pt (2)) using “magic”
methyl, CH3OSO2F, in the pursuit of water soluble complexes which may be used as
methyltransfer agents. The use of platinum as the metal is due to the potential isolation
of more stable complexes which may be crystallographically characterized.
EXPERIMENTAL
Materials and Methods
Unless otherwise indicated, all reactions were carried out under an inert argon
atmosphere using standard Schlenk and drybox techniques. Prior to their use, all
solvents were distilled using standard techniques. The parent PTA11a-b ligand was
prepared by the literature procedure as well the alkylated (PTA-CH3+)(I-)14 derivative.
The metal complexes, Ni(PTA)413, Pt(PTA)4
13, (BME-DACO)Ni76, (BME-DACH)Ni76,
(TMEDA)Pd(CH3)234b, and (TMEDA)Pd(CH3)(OPh)80 were all prepared by the
144
published procedure. All other reagents were purchased from the Aldrich Chemical Co.
and used without any additional purification.
31P NMR data were obtained using a Varian Unity+ 300 MHz NMR instrument.
Deuteratured D2O was degassed prior to its use. The 31P chemical shifts were referenced
using an external 85% H3PO4 sample. IR data was collected using a Mattson 6021 FTIR
spectrometer with DTGS and MCT detectors.
Preparation of [Ni(PTA)3((PTA-CH3)+(FSO3)-)] (3)
In a 100 mL Schlenk flask, 1 (0.200 g, 0.29 mmol) was dissolved in approximately
45 mL of acetonitrile and was subsequently cannulated over to a separate 100 mL
Schlenk flask containing CH3OSO2F (0.033 g, 0.29 mmol). The resulting milky-white
solution was stirred overnight. Subsequently, the solvent was removed, yielding a white
solid. 31P NMR (121 MHz, D2O, δ): -36.03 ((PTA-CH3)+(SO3F)-) ,
-46.52 (PTA).
Synthesis of [Ni(CO)(PTA)2((PTA-CH3)+(SO3F)-)] (4)
To a 100 mL Schlenk flask charged with 3 (0.225 g, 0.28 mmol) was added 20 mL
of H2O and was subsequently purged with CO for approximately 1 hr. The solution was
then stirred overnight after which a small aliquot was used for IR analysis. The solvent
was removed and the white solid was analyzed by 31P NMR. IR( H2O): v(CO) = 1955
cm-1. 31P NMR (121 MHz, D2O, δ): -10.25 (PTA=O), -33.60 ((PTA-CH3)+(SO3F)-), -
47.16 (PTABOUND), -101.26 (PTAFREE).
145
Synthesis of [Pt((PTA-CH3)+(SO3F)-)4] (5)
A 50 mL Schlenk flask was first charged with 2 (0.200 g, 0.24 mmol) followed by
the addition of 30 mL of CH3CN. The solution was subsequently cannulated over to a
separate 50 mL flask containing CH3OSO2F (0.083 g, 0.24 mmol), and the mixture was
stirred overnight. The solvent was then removed and analyzed by 31P NMR, which
revealed several impurities with the predominant product being 5. 31P NMR (121 MHz,
dmso-D6, δ): -62.73 (t, 1JP-Pt=3639 Hz).
Synthesis of [Ni((PTA-CH3)+(I)-)4] (6)
The synthesis of 6 was achieved by the typical displacement of the labile COD
ligands from Ni(COD)2. To a 100 mL Schlenk flask containing Ni(COD)2 (0.50 g, 1.81
mmol) was added 60 mL of toluene. To the resulting yellow solution was added (PTA-
CH3)+(I)-) (2.16 g, 7.24 mmol) in 40 mL of MeOH, by cannula technique. The resulting
solution was stirred for 1 hr, after which the white solid was collected by filtration and
washed with 2 x 5 mL of toluene. 31P NMR (121 MHz, dmso-D6, δ): -33.82.
Synthesis of [Pt((PTA-CH3)+(I)-)4] (7)
To a 100 mL Schlenk flask charged with PtCl2 (0.30 g, 1.13 mmol) and (PTA-
CH3)+(I)-) (1.01 g, 3.39 mmol) was added 30 mL of water, and the mixture was stirred
overnight. After removing the solvent, approximately 35 mL of MeOH was added
followed by 30 mL of ether, which resulted in the formation of an orange precipitate.
After filtration, the deep red mother liquor was collected and allowed to slowly
evaporate in open air, resulting in clear crystals after 4 days.
146
Synthesis of [(BME-DACO)Ni]-[Pd(CH3)(Cl)] (8)
To a 50 mL Schlenk flask containing (TMEDA)Pd(CH3)2 (0.15 g, 0.59 mmol) was
added 15 mL of CH2Cl2. A solution of (BME-DACO)Ni (0.18 g, 0.623 mmol) in 15 mL
of CH2Cl2 was added via cannula over, and the resulting dark red solution was stirred
overnight. The solvent's volume was reduced in vacuo until about 5 mL of solvent
remained. Next, 25 ml of pentane was added, resulting in the precipitation of a red solid
which was then collected by filtration. On dissolving the complex in ether and allowing
the slow diffusion of pentane into the solution, resulted in the formation of 8 as a
crystalline solid.
Synthesis of [((BME-DACH)Ni)2-µ-[Pd(CH3)2(OPh)]+[OPh]- . HOPh (9)
To a 100 mL Schlenk flask charged with (BME-DACH)Ni (0.199 g, 0.76 mmol),
was added 70 mL of benzene. A solution of (TMEDA)Pd(CH3)(OPh) (0.250 g, 0.76
mmol), 30 mL of benzene, was cannulated over, and the mixture was stirred for 72 hr.
Following the orange, insoluble solid, was separated by filtration and the solvent
pertaining to the mother liquor was removed under reduced pressure. Allowing a
benzene solution of the solid to slowly evaporate in open air resulted in crystals of 9
suitable for X-ray diffraction studies.
147
RESULTS AND DISCUSSION
Methylation Reactions of M(PTA)4 (M=Ni (1), Pt (2))
The methylation of 1 and 2 with one equivalent of CH3OSO2F was carried out at
room temperature utilizing the non-protic, polar solvent, CH3CN. These two cases
produced unique results with the use of 1 rendering a single product (eq. 6.1).
(6.1)
Unfortunately, methylation was found to take place at a single nitrogen atom of the
ligand. This type of electrophilic reaction has been observed in the preparation of the
[(PTA-CH3)+(I-)] analogue via the use of PTA with one equivalent of MeI.14 Complex 3
displays the expected two 31P NMR resonances, located at -46.48 and -35.94 ppm with a
3:1 integration ratio, respectively.
Exposing 3 to a CO pressure of 2.5 atm in water resulted in the displacement of
one PTA molecule by CO, producing the [Ni(CO)(PTA)2((PTA-CH3)+(FSO3)-)], 4,
complex. The 31P NMR spectrum displays a signal at –47.16 and –33.60 ppm which are
due to the bound PTA and the (PTA-CH3)+ species, respectively. Although the expected
2:1 PTABOUND to (PTA-CH3)+BOUND ratio was not observed, the large amount of free
PTA and an IR signal at 1955 cm-1 (similar to Ni(CO)(PTA)3) supports the formation of
4. That is, the removal of PTA appears to take place with greater ease when compared
to the methylated analogue.
Ni(PTA)4 + CH3OSO2F [Ni(PTA)3((PTA_CH3)+(FSO3)-)]CH3CNr.t., overnight
1 3
148
Carrying out the methylation reaction with 2 under identical conditions resulted
in a mixture of products. After stirring for 2hr, the sample analyzed by 31P NMR
revealed a number of splitting patterns. In addition, excess Pt(PTA)4 and the protonated
form, Pt((PTA-H)+(Cl-))4 species was observed. The latter species was initially present
in 2 due to its formation from PtCl2 and PTA. Addition of three equivalents of
CH3OSO2F to 2 resulted in yet another difficult to interpret 31P NMR spectrum.
Although no starting material was present, the spectrum displays various amounts of
coupling, some of which may be due to 31P-19F interactions. Allowing a solution of the
resulting mixture in DMSO-d6 to slowly evaporate in air resulted in the formation of
clear crystals which were subsequently analyzed by X-ray crystallography. A solid state
structure of [Pt((PTA-CH3)+(OSO2F)-)4], 5, was obtained. Crystallographic data, and
selected bond distances and angles are tabulated in Table 6.1 and Table 6.2, respectively.
A thermal ellipsoid representation showing 50% probability is provided in Figure 6.2.
Surprisingly, one nitrogen atom corresponding to each PTA ligand is methylated, which
was not expected due to the 3:1 phosphine to metal stoichiometry. The platinum metal
center exhibits the typical tetrahedral geometry associated with a group 10 metal center
in the “0” oxidation state. The four –OSO2F groups are in close proximity to the
nitrogen atoms, and the change associated with the methylated C(12)-N(4) and C(10)-
N(4) bond distances is clearly evident, as an average 0.07 Ả lengthening occurs when
compared to the non-alkylated C-N group (i.e., C(10)-N(5): 1.49(3) Ả) of PTA. The
Pt(1)-P(x) (x=1-4) bond distances are found to have an average value of 2.268 Ả. The
149
Table 6.1. Crystallographic data and data collection parameters for compounds 5, 7, 8', and 9.
5 7 8' 9
Cryst syst monoclinic Triclinic orthorhombic Monoclinic
space group P2(1)/c P-1 Pmn2(1) P2(1)/c
V, Å3 4780(10) 2216.9(4) 926.3(8) 4024(5)
Z 4 2 2 8
a, Å 14.602(18) 12.8106(14) 12.234(6) 13.276(10)
b, Å 13.653(17) 12.8389(14) 9.291(5) 19.674(14)
c, Å 24.28(3) 13.9945(15) 8.149(4) 16.634(11)
α, deg — 98.512(2) — —
β, deg 99.05(2) 96.086(2) — 112.139(15)
γ, deg — 100.542(2) — —
T, K 110 110 110 110
d(calc), g/cm3 1.801 2.156 1.903 1.801
Abs coeff, mm-1 3.330 6.139 2.624 2.054 R,a % [I > 2σ (I)] 7.72 8.84 4.45 9.62
Rw,a % 20.63 9.45 4.57 24.41 a R = Σ || Fo | – | Fc || / ΣFo and RwF = {[Σw(Fo – Fc)2] / ΣwFo
2}½
150
Table 6.2. Selected bond distances (Å) and angles for compounds 5, 7, 8', and 9.a
Compound 5
Pt(1)-P(1) 2.266(5) Pt(1)-P(4) 2.275(7) N(3)-C(6) 1.56(3) Pt(1)-P(2) 2.261(5) N(3)-C(25) 1.46(3) N(1)-C(4) 1.42(3) Pt(1)-P(3) 2.270(7) N(3)-C(4) 1.52(3) N(1)-C(5) 1.49(3) P(1)-Pt(1)-P(2) 107.46(19) P(2)-Pt(1)-P(3) 108.3(3) P(1)-Pt(1)-P(3) 111.5(3) P(3)-Pt(1)-P(4) 110.16(19) P(1)-Pt(1)-P(4) 109.9(3)
Compound 7 Pt(1)-P(1) 2.260(3) Pt(1)-P(4) 2.264(3) N(4)-C(10) 1.509(19) Pt(1)-P(2) 2.262(3) N(4)-C(25) 1.491(19) N(5)-C(10) 1.455(19) Pt(1)-P(3) 2.253(3) N(4)-C(12) 1.536(19) N(5)-C(11) 1.468(18) P(1)-Pt(1)-P(2) 110.33(11) P(2)-Pt(1)-P(3) 109.49(11) P(1)-Pt(1)-P(3) 107.97(11) P(3)-Pt(1)-P(4) 110.10(10) P(1)-Pt(1)-P(4) 110.43(11)
Complex 8’ Ni(1)-S(1) 2.179(3) Pd(1)-S(1) 2.368(3) Pd(1)-Cl(1) 2.275(19) Ni(1)-N(1) 1.960(8) Pd(1)-C(1) 2.12(5) Ni(1)-Pd(1) 2.802(2) S(1)-Ni(1)-N(1) 90.9(2) S(1)-Pd(1)-S(1A) 77.03(12) N(1)-Ni(1)-N(1A) 91.4(5) S(1)-Pd)1)-Cl(1) 98.3(5) S(1)-Ni(1)-S(1A) 85.14(16)
151
Table 6.2 (Continued).
Compound 9 Ni(1A)-S(1A) 2.153(8) Ni(1B)-N(1B) 1.89(2) Pd(1)-C(1) 2.02(2) Ni(1A)-S(2A) 2.155(8) Ni(1B)-N(2B) 1.930(19) Pd(1)-O(1) 2.104(15) Ni(1A)-N(1A) 1.91(2) Pd(1)-S(1A) 2.275(7) Pd(2)-C(2) 1.96(2) Ni(1A)-N(2A) 1.93(2) Pd(1)-S(1B) 2.283(7) Pd(2)-O(1) 2.089(17) Ni(1B)-S(1B) 2.122(7) Pd(2)-S(2A) 2.306(7) Ni(1B)-S(2B) 2.130(8) Pd(2)-S(2B) 2.271(7) S(1A)-Ni(1A)-N(2A) 168.9(7) S(1A)-Pd(1)-C(1) 97.2(7) S(2A)-Ni(1A)-N(1A) 170.0(7) S(1B)-Pd(1)-C(1) 86.2(7) S(1A)-Ni(1A)-N(1A) 90.2(7) C(1)-Pd(1)-O(1) 178.1(9) S(2A)-Ni(1A)-N(2A) 90.9(8) S(1A)-Pd(1)-O(1) 83.8(5) S(1A)-Ni(1A)-S(2A) 97.5(3) S(1B)-Pd(1)-O(1) 92.8(5) N(1A)-Ni(1A)-N(2A) 80.7(10) S(2A)-Pd(2)-C(2) 96.7(8) S(1B)-Ni(1B)-N(2B) 171.7(7) S(2B)-Pd(2)-C(2) 87.7(8) S(2B)-Ni(1B)-N(1B) 173.5(7) C(2)-Pd(2)-O(1) 175.6(10) S(1B)-Ni(1B)-S(2B) 94.5(3) S(2A)-Pd(2)-O(1) 81.3(5) N(1B)-Ni(1B)-N(2B) 83.0(9) S(2B)-Pd(2)-O(1) 94.9(5) S(2B)-Ni(1B)-N(2B) 90.7(7) Pd(1)-O(1)-Pd(2) 108.7(7) a Estimated standard deviations are given in parenthesis.
152
Figure 6.2. Thermal ellipsoid representation of Pt[(PTA-CH3+)(OSO2F-)]4 (5) showing 50% probability
(OSO2F- groups omitted for clarity).
153
P(1)-Pt(1)-P(2) and P(3)-P(1)-P(4) angles were found to be 107.46(19) and 110.16(19)º,
respectively.
Alternatively, methylation reactions involving the [Ni((PTA-CH3)-(I)-)4], 6,
derivative was carried out to attempt to methylate the metal center on an already
alkylated PTA ligand. The preparation of 6 was accomplished by the displacement of
the labile ligands of Ni(COD)2 with four equivalents of (PTA-CH3+)(I-) (eq. 6.2).
Ni(COD)2 + 4 (PTA-CH3
+)(I-) Ni((PTA-CH3+)(I-))4
Toluene/MeOH25o C, 1 hr
6 (6.2)
The 31P NMR resonance associated with 6 lies at -33.82 ppm, in DMSO-d6.
Unfortunately, subjecting 6 to one equivalent of CH3OSO2F resulted in no reaction after
stirring at room temperature for approximately 2 hr. The platinum analogue to 6 was
also prepared by the reduction of PtCl2 with five equivalents of (PTA-CH3+)(I-) in water
(eq. 6.3).
(6.3)
During the course of the reaction, a deep red solution was observed, which is indicative
of the disubstituted PtCl2 species. After filtration, the solid was analyzed by 31P NMR in
DMSO-d6 and revealed a mixture of products. However, allowing the DMSO-d6
solution to stand in air for 4 days, resulted in the formation of large, clear crystals that
PtCl2 + 5 (PTA_CH3+)(I-) Pt((PTA_CH3
+)(I-))4H2O25o C, 12 hr
7
154
were analyzed by X-ray crystallography. The solid state structure confirmed the
formation of 7. Crystallographic data, and selected bond distances and angles for
complex 7 are tabulated in Table 6.1 and Table 6.2, respectively. A thermal ellipsoid
representation showing 50% probability is provided in Figure 6.3. Due to exposure to
moisture exposure during crystal growth, three water molecules are found in the
asymmetric unit. Surprisingly, no hydrogen bonding to the surrounding nitrogen atoms
of the phosphine was observed. The platinum metal center exhibits tetrahedral geometry
with the P(1)-Pt(1)-P(2) and P(3)-Pt(1)-P(4) angles having values of 110.33(11) amd
110.10(10)˚, respectively. The average Pt(1)-P(x) (x = 1-4) bond distance was found to
be 2.260 Å, and is almost identical to that found in 6. Additionally, the C(2)-N(3) and
C(6)-N(3) bond distances were found to be approximately 0.04 Å longer than the non-
alkylated N-C bond distances. This type of bond lengthening in the PTA framework has
been observed in other PTA derivatives such as in the Pt((PTA-H+)(Cl-))4 analogue.12,32
Bimetallic Nickel and Palladium Complexes
Initially, the strategy for the formation of the bimetallic [(N2S2)Ni]-[Pd(CH3)(SR)]
complex involved the displacement of the labile TMEDA ligand from
(TMEDA)Pd(CH3)2 precursor by the (BME-DACO)Ni complex (Scheme 6.2).
Hydrolysis of a single CH3 group in 8 to afford the thermodynamically stable CH4 (g)
side-product using one equivalent of HSPh would yield the desired dimer. Due to the
low solubility of (BME-DACO)Ni complex in most organic solvents, apart from lower
molecular weight alcohols, methylene chloride was employed as the reaction medium.
155
Figure 6.3. Thermal ellipsoid representation of Pt[(PTA-CH3+)(I-)]4 (7) showing 50% probability.
156
Scheme 6.2
N SNi
N S+
N
N
Pd
CH3
CH3
TMEDA(TMEDA)Pd(CH3)2n=0 (BME-DACH)Ni
n=1 (BME-DACO)Ni
PdCH3
CH3
8
CH2Cl2
ClCH2CH3
8'
N SNi
N S
n
n
n
PdCH3
Cl
N SNi
N S
157
The addition of one equivalent of (TMEDA)Pd(CH3)2, in toluene, to the purple (BME-
DACO)Ni complex, in methylene chloride, resulted in an immediate color change to
deep red. Crystals were obtained by the slow diffusion of pentane into a CH2Cl2
solution of the red product. Unfortunately, 8 is reactive toward chlorinated solvents,
replacing a methyl group with chlorine, forming the [Pd]-Cl derivative, 8’.
Crystallographic data, and selected bond distances and angles are provided in Table 6.1
and Table 6.2, respectively. A thermal ellipsoid representation of 8’ showing 50%
probability is presented in Figure 6.4. The disordered methyl and chlorine atoms are
modeled as populating each site approximately 50% of the time. The nickel metal center
adopts a slightly distorted square planar geometry, with the N(1A)-Ni(1)-S(1) bond
angle exhibiting an angle of 169.9(3)º. The N(1A)-Ni(1)-N(1) bond angle has a value of
91.4(5)º and is approximately 6.3º larger than the S(1A)-Ni(1)-S(1) angle. The S(1A)-
Ni(1)-S(1) bond angle is clearly affected by the ligation of the two sulfur atoms to
palladium, as an approximate 5º decrease in this angle is observed when compared to
free (BME-DACO)Ni.76 The Ni(1)-S(1) bond length was found to be 2.179(3) Ả and is
nearly identical that seen in (BME-DACO)Ni. The palladium metal center also exhibits
square planar geometry with the S(1A)-Pd(1)-C(1) and S(1)-Pd(1)-Cl(1A) bond angles
having a value of 173.4(16)º. The Pd(1)-S(1) and Pd(1)-C(1) bond distances were found
to be 2.368(3) and 2.12(5) Ả, respectively, while the Ni(1)-Pd(1) bond distance was
found to have a value of 2.802 Ả. An important geometrical aspect of the dimer
involves the location of the palladium metal center with respect to the nickel metal, as
158
Figure 6.4. Thermal ellipsoid representation of (BME-DACO)Ni-Pd(CH3)(Cl) (8’) showing 50% probability.
159
the plane formed by the N2S2 fragment is at a 79.92º angle with respect to that formed by
the S(1), S(1A), C(1), and Cl(1) atom framework of palladium.
Due to the reactivity of the complex toward chlorinated solvents, the attempted
synthesis of (TMEDA)Pd(CH3)(SPh) was carried out in order to subsequently expose the
complex to (BME-DACH)Ni using a chlorinated solvent medium. However, the
reaction between (TMEDA)Pd(CH3)2 and one equivalent of HSPh resulted in an
insoluble aggregate. Due to this difficulty, the phenoxy derivative was prepared by
reacting palladium (TMEDA)Pd(CH3)2 and one equivalent of HOPh in ether.80 Using
this palladium precursor, (TMEDA)Pd(CH3)(OPh), with one equivalent of the (BME-
DACH)Ni complex (BME-DACH: n = 0 in Scheme 6.2) in methylene chloride and
benzene, yielded a surprising result. Red crystals of the complex, 9, were isolated and
analyzed by X-ray crystallography. Crystallographic data, and selected bond distances
and angles are tabulated in Table 6.1 and Table 6.2, respectively. A thermal ellipsoid
representation of 9 showing 50% probability is given in Figure 6.5. The overall shape of
the complex is a step with the palladium metal center forming an "A" frame using two
methyl groups and a phenoxy ligand in the apex position. The step is formed by the
S(1A), S(2A), S(1B), and S(2B) plane with the two S(1A)-Pd(1)-S(1B) and S(2A)-
Pd(2)-S(2B) angles being 175.8(3) and 171.0(3)˚, respectively. Both nickel metal
centers exhibit a slightly distorted square planar geometry with the Ni(1A)-Ni(1A)-
S(2A), N(2A)-Ni(1A)-S(1A), N(1B)-Ni(1B)-S(2B), and N(2B)-Ni(1B)-S(1B) having
values of 170.0(7), 168.9(7), 173.6(7), and 171.7(7)˚, respectively. The N-Ni-N and
160
Figure 6.5. Thermal ellipsoid representation of [(BME-DACH)Ni]2-[Pd(CH3)]2(OPh) (9) showing 50% probability.
161
S-Ni-S were found to be nearly identical to those found in the free (BME-DACH)Ni
complex.76 The Pd(2)-S(2A)-Ni(1A), Pd(1)-S(1A)-Ni(1A), Pd(1)-S(1B)-Ni(1B), and
Pd(2)-S(2B)-Ni(1B) exhibit bond angles of 106.7(3), 110.4(3), 107.2(3), and 104.1(3)˚,
respectively, and face in opposite directions. The planes formed by the N(1A), N(2A),
S(1A), and S(2A) atoms are at approximately 59.29˚ with respect to that formed by the
S(1A), Pd(1), S(2A) and Pd(2) atoms (Figure 6.6). The palladium metal center also
exhibits distorted square planar geometry with corresponding C(1)-Pd(1)-O(1) and C(2)-
Pd(2)-O(1) bond angles of 178.1(9) and 175.4(10)˚, respectively. The plane formed by
the phenyl ring is paralleled to that formed by the "A" frame. The two nickel metal
centers, Ni(1A) and Ni(1B), lie approximately 0.112 and 0.073 Å from their respected
N2S2 plane. The Pd(1)-C(1) and Pd(2)-C(2) bond distance were found to be 2.02(2) and
1.95(2) Å, respectively. Asobserved in Figure 6.5, one deprotonated phenolic ligand is
present in the asymmetric unit for charge balance purposes. A surprising aspect of 9
involves the stable nature of the complex, as the Pd-CH3 bond is not hydrolyzed in the
presence of atmospheric moisture.
CONCLUDING REMARKS
The methylation of Ni(N2S2) at the nickel metal center in the active site of ACS has
been shown to occur through a methyl cobalamine protein (CH3-[CoIII]. Herein, we have
focused on the synthesis of a water-soluble organometallic [M]-CH3 methyl cobalamine
analogue bearing PTA as the water-solubilizing ligand. However, all attempts to prepare
162
Figure 6.6. Selected plane angles of complex [(BME-DACH)Ni]2-[Pd(CH3)]2(OPh) (9).
Pd(1)
Pd(2) S(2A)
S(1A)
N(2A)
N(1A)
θ=120.71
S(1B)
S(2B) Pd(2)
Pd(1)
N(2B)
N(1B)
θ=112.54
Pd(1)
Pd(2) S(2A)
S(1A)
O(1)
θ=80.16
163
these complexes via the oxidative addition using CH3OSO2F were unsuccessful, and
resulted in methylation of the PTA nitrogen atom. Furthermore, attempting to methylate
the methyl-containing PTA analogue, (PTA-CH3+)(I)-, 6, resulted in no reactivity.
Perhaps the added sterically encumbering methyl groups on four PTA units prohibits the
formation of the trigonal bipyramidal [Ni]-CH3 species, which would be analogous to
the [CH3Ni(PMe3)4]+[B(C6H5)4]- complex.81 Carrying out identical reactions using
platinum as the metal center was also unsuccessful and yielded a mixture of products, as
determined by 31P NMR. Out of these preliminary studies, complexes 5 and 7 were
isolated as colorless crystals. Crystallographic data indicates 5 and 7 to be nearly
identical with respect to bond distances and angles and demonstrate the lengthening of
the alkylated N-C bond when compared to the other non-alkylated N-C bonds. It is
evident from these studies that a different approach is needed to afford PTA based [M]-
CH3 complexes. An alternative route parallels the synthesis of
[BrNi(PMe3)4]+[B(C6H5)4]- which can then be methylated using CH3Li.82
Modeling the active site depicted in Figure 6.1 with organometallic complexes is of
great interest due to the potential to simplify the catalytic production of thioesters via a
similar route. Additionally, finding a suitable bimetallic nickel species which
accomplishes this type of reaction would further support and shed light into the ACS
mechanistic pathway. The attempted synthesis of complexes of the type 8 was carried
out using [(BME-DACO)Ni] with one equivalent of (TMEDA)Pd(CH3)2. Unfortunately,
it was shortly realized that complexes of the type 8 react with halogenated solvents to
form the undesired [Pd]-Cl analogues, 8’. Complex 8’ was characterized by X-ray
164
crystallography and shows very unique binding of the nickel complex to the palladium
metal center with the N2S2 plane being approximately 10º from forming a right angle
with respect to the corresponding plane associated with the palladium coordination
sphere. Furthermore, from these preliminary studies it is evident that the preparation of
such a bimetallic complex is possible without the drawback of forming other side
products such as trimetallic complexes.75 Additionally, known [Ni]-SR complexes may
be used to directly produce the desired organometallic model. For example, Holm and
Tucci have reported the synthesis of a nickel complex incorporating a variety of thiols,
which was shown to insert CO followed by reductive elimination to afford Ni(bpy)(CO)2
(bpy=2,2’-bipyridyl) and the corresponding thioester (Figure 6.7).77
Figure 6.7. Holm’s Ni(bpy)(CH3)(SR) complex.
Their in-depth investigation on these types of complexes also reveals the ease in which
most of the derivatives crystallize, thereby affording important structural data.
The use of the (TMEDA)Pd(CH3)(OPh) as a reagent, however, led to the synthesis
of the trimetallic species, 9, upon exposure to moisture during crystal growth. The
N
N
Ni
CH3
SR
165
complex adopts a very unique structural arrangement, taking the form of a step with the
two nickel metal centers located at each extremity. Additionally, the palladium metal
center forms part of the “A” frame. One interesting factor is the stability of the Pd-CH3
bond toward hydrolysis.
Overall, the synthesis of (N2S2)Ni-M(CH3)(SR) (M=Ni, Pd) using (BME-
DACO)Ni complexes are feasible if the correct reaction conditions are met, including
the use of the appropriate solvent medium. Once these types of complexes are produced,
the CO insertion study may be conducted to attempt to determine the binding mode of
CO. That is, although one would expect CO to bind to the nickel metal center
containing the CH3 group, the possible binding of CO to the (N2S2)Ni prior to insertion
may occur and be of monumental importance to the ACS Acetyl-CoA synthesis process.
166
CHAPTER VII
CONCLUSIONS
The work presented in this dissertation is a compilation of two main areas:
Organometallic aqueous chemistry (Chapter II-III) and the coupling of CO2 and
epoxides using a salen based catalyst (Chapter IV-V). In the former, we report the
synthesis of group 10 salicylaldiminato complexes bearing the water-soluble 1,3,5-
triaza-7-phosphaadamantane (PTA) phosphine ligand (Chapter II). Of importance is the
air stability and good donating properties of PTA, including its small cone angle (~102˚)
which enables it to effectively stabilize low valent group 10 metals in aqueous
medium.11,12 The nickel salicylaldiminato PPh3 derivatives, developed by Grubbs and
coworkers, have been shown to be effective in the polymerization of ethylene, often
exhibiting activities comparable to traditional Ziegler-Natta systems.9 One of the main
drawbacks, however, is the need for a phosphine scavenger in order to produce the
active catalytic species. Herein, we have replaced the hydrophobic PPh3 with PTA in an
effort to trap the dissociated water-soluble phosphine in the aqueous medium by
employing a biphasic toluene/water solvent system. The PTA complexes can be easily
synthesized by the ligand exchange reaction between PPh3 and PTA using Grubbs'
catalyst in a homogeneous toluene/methanol solvent system. Alternatively, a direct
approach may be used in which (TMEDA)M(CH3)2 (M= Ni, Pd) is reacted with one
equivalent of the salicylaldimine and PTA, respectively. The first route produces the
desired product in good yields, while the latter often affords near quantitative yields for
several of these derivatives. Throughout the chapter, we present numerous solid state
167
structures, as these complexes all crystallize well using the traditional protocol of
allowing the slow diffusion of pentane into a toluene or methylene chloride solution of
the complex. An important point to make with regards to catalyst design is the
significance of the mono-ligated salicylaldiminato complex, as the bis derivative leads to
deactivation during polymerization.
Unfortunately, all polymerization attempts resulted in a completely inactive
system. This is presumably due to a lack of phosphine dissociation which can be
attributed to the strong M-P bond strength. The concept of forming the active species
via this mechanism, however, is viable if the correct choice of phosphine is made.
Therefore, these investigations can be viewed as a stepping stone to the production of
active catalytic species for a variety of processes via the use of a biphasic medium. As
far as this particular research is concerned, the use of less donating water-soluble
phosphines with similar dissociation energy as that seen with PPh3 should prove this
technique successful.
The subject devoted to chapter III concerns the full characterization of the novel
water-soluble phosphine, 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane
(DAPTA), in addition to the preparation of several group 6 and group 10 complexes
incorporating the ligand.11d One of the most surprising results involves the water-
solubility associated with DAPTA, as a 7.4 M solution was accomplished which is far
more water-soluble than the commercially used TPPTS ligand (see Figure 3.2). This
PTA derivative is easily prepared by the direct acylation of PTA using acetic anhydride
in an aqueous medium. The corresponding oxide derivative is also readily prepared by
168
the same acylation reaction with PTA oxide. Two group 10 metal complexes
incorporating DAPTA were prepared. The tetrakis(DAPTA)nickel derivative was easily
synthesized by the typical protocol of ligand substitution of Ni(COD)2 with four
equivalents of DAPTA. Although the complex is formed in near quantitative yields, the
water-solubility of the white powder is non-existent, and an explanation for this
observation still remains to be addressed. The palladium salicylaldiminato derivative is
identical to the PTA analogues described in Chapter II. Unfortunately, using this
derivative in the aforementioned biphasic medium process would render an inactive
system due to the stronger M-P bond strength than that associated with PTA, as was
observed by NMR data. The binding mode in each of the complexes mentioned above
closely resembles that observed with PTA, and is further supported by the synthesis of
the tungsten and chromium pentacarbonyl complexes, M(CO)5(DAPTA). A comparison
of the solid state data to that obtained with the PTA derivatives clearly indicates similar
binding mode and strength. The purpose of this subject was well realized in that this
unexplored ligand was fully characterized by NMR and solid state data, and adds
another potential ligand for use in aqueous catalysis.
The second main topic considered concerns the catalytic process of coupling CO2
and epoxides utilizing Cr(salen)X (X = Br, OPh) catalysts (Chapter IV). This type of
catalysis involving chromium as the metal center with the tetradentate salen framework
was first observed in our laboratories for the production of high molecular weight
polycarbonate.23 The idea behind using such catalysts originated from the work of
Jacobsen, as he demonstrated these complexes to be active in the asymmetric ring
169
opening of epoxides to afford products in high enantiomeric excess.24 Herein, we have
focused on increasing the activity of the previously reported catalysts by not only
replacing the nucleophile bound to chromium, but also incorporating more electron
donating Lewis bases (i.e., phosphines). In this chapter, we report the most active
systems to date (compared to the previously published results using the Cr(salen)Cl23),
affording activities on the order of 109 mol CHO consumed . mol Cr-1 . hr-1 with the use
of X = Br and L = PCy3 as the cocatalyst. Monitoring the copolymerization in situ using
and ASI 1000 ReactIR probe equipped with a high pressure stainless steel Parr reactor,
we have observed the dramatic changes in rate as the phosphine cocatalyst is varied,
with the most active being PCy3. The order of increased activity as a function of
phosphine was found to be: PCy3>P(p-toly)3>PPh3.
Catalysts design aspects were also investigated by looking at similar chromium
derivatives incorporating another Schiff base ligand framework. In the aforementioned
Cr(salen)X catalysts, the nucleophile resides trans to the binding of epoxide or
cocatalyst, and enchainment presumably takes place on one face of the ligand framework
(see Figure 4.12). A chromium bis-salicylaldiminato complex was prepared in which
substrate binding is in a cis orientation relative to the nucleophile (e.g., polymer chain).
Important concepts to take from these studies correspond to not only lower activities due
the inability to use cocatalysts (use of cocatalysts effectively block binding of substrate),
but also the production of copolymer with large amounts of polyether linkages due to
repeated epoxide ring-opening steps.
170
Investigating the potential use of other metals in this copolymerization process is
considered in Chapter V, as Fe(salen)OR (OR= 2,6-diphenylphenoxy, acac) derivatives
were prepared. To our knowledge, this is the first report involving the synthesis of any
phenoxy derivative in iron salen chemistry. The two aforementioned derivatives were
characterized by obtaining their solid state structures, and dramatic differences are
clearly observed when a monodentate or bidentate anionic ligand is employed. Using
the bidentate acetylacetonate ligand, the complex adopts a very distorted octahedral
geometry, and points toward the desire for the species to be square pyramidal as
observed with chromium derivatives (see Chapter IV). Unfortunately, both of these
complexes were inactive in the copolymerization of CO2 and epoxides. A probable
cause for the inactivity may result from using OPh as the initiator. These OPh groups
have been found to insert CO2 orders of magnitude slower than corresponding alkoxy,
OR, functionalities.60 Of course, the lack of activation of epoxides by the iron metal
center cannot be ruled out. The µ-oxo dimer was also prepared by the hydrolysis of the
[Fe(salen)(N(Si(CH3)3)2)] intermediate, and characterized by X-ray crystallography.
Several key structural aspects are reported, including its nearly linear Fe(1)-O(3)-Fe(1A)
unit.
Miscellaneous methylation reactions and synthesis of model Acetyl Coenzym-A
Synthase complexes are also reported (Chapter VI). The synthesis of novel group 10
PTA complexes incorporating a methylated metal center was attempted by using
CH3OSO2F as the methylating agent. Unfortunately, all attempts were unsuccessful and
resulted in methylation of the nitrogen atom on the PTA ligand. Using the already
171
methylated PTA complexes was found to be unreactive toward CH3OSO2F. Although
all reactions did not produce the desired products, novel platinum, Pt(PTA-CH3+)(X-)
(X=OSO2F, I), complexes were characterized by X-ray crystallography. Both
complexes exhibit similar characteristics; for example, the alkylated N-C bonds are all
slightly longer than those associated with no substitution.
The synthesis of model bimetallic ACS complexes was also attempted by using
(BME-DACO)Ni and (BME-DACH)Ni as the N2S2 core, along with
(TMEDA)Pd(CH3)2. Although the desired bimetallic structure was obtained, the final
(N2S2)Ni-Pd(CH3)2 product ultimately reacts with the chlorinated medium and results in
the (N2S2)Ni-Pd(CH3)(Cl) derivative. Although unsuccessful, these studies may be used
as a learning tool to better develop a suitable reaction protocol for the production of
these bimetallic complexes. Alternatively, the use of other precursors to replace the
aforementioned palladium species, should lead to the desired product. In fact, nickel
complexes such as those prepared by Holm, may be an attractive route.77 Synthesis of
[Pd]-OPh complexes resulted in a very unique trimetallic product when exposed to air
(see Figure 6.5). The complex takes the form of a step with an built-in "A" frame. A
complete description of the solid state data is also included in this chapter.
172
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APPENDIX A
BOND DISTANCES AND ANGLES CORRESPONDING TO SOLID STATE
STRUCTURES IN CHAPTER II*
Table A.1. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for trans-(PPh3)2Ni(Ph)(Cl). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Ni(1) 8384(1) 512(1) 7350(1) 15(1) Cl(1) 10390(1) 759(1) 7027(1) 22(1) P(1) 8514(1) 2349(1) 7102(1) 15(1) P(2) 8132(1) -1317(1) 7677(1) 15(1) C(1) 6617(2) 234(2) 7379(1) 17(1) C(2) 6040(2) 501(2) 8208(2) 21(1) C(3) 4734(2) 289(2) 8183(2) 27(1) C(4) 3966(2) -191(2) 7324(2) 32(1) C(5) 4507(2) -465(2) 6489(2) 28(1) C(6) 5812(2) -257(2) 6514(2) 23(1) C(7) 7308(2) 3074(2) 7465(1) 16(1) C(8) 6099(2) 2677(2) 6959(2) 22(1) C(9) 5143(2) 3169(2) 7204(2) 26(1) C(10) 5373(2) 4092(2) 7958(2) 25(1) C(11) 6568(2) 4510(2) 8461(2) 23(1) C(12) 7532(2) 4004(2) 8227(1) 19(1) C(13) 8570(2) 2594(2) 5831(1) 17(1) C(14) 8799(2) 1757(2) 5143(1) 19(1) C(15) 8858(2) 1955(2) 4175(2) 24(1) C(16) 8678(2) 2983(2) 3900(2) 29(1) C(17) 8462(2) 3829(2) 4582(2) 31(1) C(18) 8406(2) 3640(2) 5550(2) 24(1) C(19) 9988(2) 3315(2) 7746(1) 15(1) C(20) 10207(2) 3267(2) 8739(1) 19(1) C(21) 11330(2) 3930(2) 9269(1) 20(1) _______________ * Appear in the order in which they are described in the chapter.
183
C(22) 12269(2) 4633(2) 8807(2) 20(1) C(23) 12058(2) 4671(2) 7817(1) 21(1) C(24) 10928(2) 4023(2) 7290(1) 18(1) C(25) 9506(2) -1681(2) 8243(1) 16(1) C(26) 10463(2) -801(2) 8824(1) 21(1) C(27) 11448(2) -1082(2) 9327(2) 25(1) C(28) 11494(2) -2243(2) 9264(1) 23(1) C(29) 10549(2) -3125(2) 8689(1) 22(1) C(30) 9568(2) -2841(2) 8182(1) 19(1) C(31) 7649(2) -2330(2) 6540(1) 16(1) C(32) 8037(2) -1910(2) 5679(1) 19(1) C(33) 7690(2) -2633(2) 4794(2) 24(1) C(34) 6947(2) -3783(2) 4756(2) 24(1) C(35) 6565(2) -4219(2) 5604(2) 23(1) C(36) 6913(2) -3500(2) 6490(1) 19(1) C(37) 6941(2) -1914(2) 8481(1) 16(1) C(38) 5652(2) -2242(2) 8157(2) 21(1) C(39) 4749(2) -2610(2) 8788(2) 26(1) C(40) 5127(2) -2649(2) 9753(2) 27(1) C(41) 6397(2) -2334(2) 10086(2) 25(1) C(42) 7308(2) -1969(2) 9458(1) 20(1) _______________________________________________________________________
Table A.2. Bond lengths [Å] and angles [°] for trans-(PPh3)2Ni(Ph)(Cl). _______________________________________________________________________ Ni(1)-C(1) 1.887(2) Ni(1)-P(1) 2.2114(6) Ni(1)-P(2) 2.2155(6) Ni(1)-Cl(1) 2.2327(6) P(1)-C(19) 1.822(2) P(1)-C(13) 1.8251(19) P(1)-C(7) 1.833(2) P(2)-C(31) 1.826(2) P(2)-C(25) 1.829(2) P(2)-C(37) 1.8334(19) C(1)-C(2) 1.400(3) C(1)-C(6) 1.409(3) C(2)-C(3) 1.388(3) C(3)-C(4) 1.383(3) C(4)-C(5) 1.387(3) C(5)-C(6) 1.388(3) C(7)-C(8) 1.395(3) C(7)-C(12) 1.398(3)
C(8)-C(9) 1.378(3) C(9)-C(10) 1.384(3) C(10)-C(11) 1.381(3) C(11)-C(12) 1.391(3) C(13)-C(14) 1.385(3) C(13)-C(18) 1.394(3) C(14)-C(15) 1.395(3) C(15)-C(16) 1.376(3) C(16)-C(17) 1.381(3) C(17)-C(18) 1.391(3) C(19)-C(24) 1.388(3) C(19)-C(20) 1.395(3) C(20)-C(21) 1.382(3) C(21)-C(22) 1.390(3) C(22)-C(23) 1.387(3) C(23)-C(24) 1.382(3) C(25)-C(30) 1.389(3) C(25)-C(26) 1.399(3)
184
C(26)-C(27) 1.382(3) C(27)-C(28) 1.384(3) C(28)-C(29) 1.389(3) C(29)-C(30) 1.384(3) C(31)-C(36) 1.399(2) C(31)-C(32) 1.399(2) C(32)-C(33) 1.384(3) C(33)-C(34) 1.384(3) C(34)-C(35) 1.388(3) C(35)-C(36) 1.383(3) C(37)-C(38) 1.394(3) C(37)-C(42) 1.402(3) C(38)-C(39) 1.389(3) C(39)-C(40) 1.386(3) C(40)-C(41) 1.378(3) C(41)-C(42) 1.391(3) C(1)-Ni(1)-P(1) 89.20(6) C(1)-Ni(1)-P(2) 87.04(6) P(1)-Ni(1)-P(2) 175.33(3) C(1)-Ni(1)-Cl(1) 169.76(6) P(1)-Ni(1)-Cl(1) 90.05(2) P(2)-Ni(1)-Cl(1) 94.13(2) C(19)-P(1)-C(13) 105.62(9) C(19)-P(1)-C(7) 103.97(9) C(13)-P(1)-C(7) 101.21(9) C(19)-P(1)-Ni(1) 108.67(6) C(13)-P(1)-Ni(1) 114.42(7) C(7)-P(1)-Ni(1) 121.47(6) C(31)-P(2)-C(25) 105.23(9) C(31)-P(2)-C(37) 104.15(9) C(25)-P(2)-C(37) 100.16(9) C(31)-P(2)-Ni(1) 108.74(6) C(25)-P(2)-Ni(1) 117.94(6) C(37)-P(2)-Ni(1) 119.01(7) C(2)-C(1)-C(6) 116.9(2) C(2)-C(1)-Ni(1) 124.28(15) C(6)-C(1)-Ni(1) 118.76(16) C(3)-C(2)-C(1) 121.7(2) C(4)-C(3)-C(2) 120.2(2) C(3)-C(4)-C(5) 119.6(2) C(4)-C(5)-C(6) 120.2(2) C(5)-C(6)-C(1) 121.3(2) C(8)-C(7)-C(12) 117.95(19)
C(8)-C(7)-P(1) 118.51(15) C(12)-C(7)-P(1) 123.54(16) C(9)-C(8)-C(7) 121.5(2) C(8)-C(9)-C(10) 120.1(2) C(11)-C(10)-C(9) 119.4(2) C(10)-C(11)-C(12) 120.8(2) C(11)-C(12)-C(7) 120.2(2) C(14)-C(13)-C(18) 119.49(18) C(14)-C(13)-P(1) 120.49(15) C(18)-C(13)-P(1) 120.01(16) C(13)-C(14)-C(15) 120.31(19) C(16)-C(15)-C(14) 119.9(2) C(15)-C(16)-C(17) 120.2(2) C(16)-C(17)-C(18) 120.2(2) C(17)-C(18)-C(13) 119.8(2) C(24)-C(19)-C(20) 118.92(18) C(24)-C(19)-P(1) 123.56(15) C(20)-C(19)-P(1) 117.36(14) C(21)-C(20)-C(19) 120.79(18) C(20)-C(21)-C(22) 119.97(19) C(23)-C(22)-C(21) 119.29(19) C(24)-C(23)-C(22) 120.75(18) C(23)-C(24)-C(19) 120.27(18) C(30)-C(25)-C(26) 118.53(19) C(30)-C(25)-P(2) 121.21(15) C(26)-C(25)-P(2) 119.99(15) C(27)-C(26)-C(25) 120.62(19) C(26)-C(27)-C(28) 120.22(19) C(27)-C(28)-C(29) 119.7(2) C(30)-C(29)-C(28) 119.96(19) C(29)-C(30)-C(25) 120.94(18) C(36)-C(31)-C(32) 118.64(18) C(36)-C(31)-P(2) 123.27(14) C(32)-C(31)-P(2) 118.08(14) C(33)-C(32)-C(31) 120.74(17) C(34)-C(33)-C(32) 119.89(18) C(33)-C(34)-C(35) 120.15(19) C(36)-C(35)-C(34) 120.12(18) C(35)-C(36)-C(31) 120.44(18) C(38)-C(37)-C(42) 118.63(18) C(38)-C(37)-P(2) 120.84(15) C(42)-C(37)-P(2) 120.38(16) C(39)-C(38)-C(37) 120.72(19) C(40)-C(39)-C(38) 119.9(2)
185
C(41)-C(40)-C(39) 120.2(2) C(40)-C(41)-C(42) 120.2(2)
C(41)-C(42)-C(37) 120.3(2)
_______________________________________________________________________ Table A.3. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 1a. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Ni(1) 6630(1) 7588(1) 7368(1) 17(1) P(1) 7945(1) 8491(1) 6520(1) 16(1) N(1) 5547(2) 6730(2) 8150(1) 16(1) N(2) 2348(3) 9860(2) 9884(2) 32(1) O(1) 6014(2) 8962(2) 7663(1) 21(1) O(2) 1708(3) 9074(2) 10220(2) 54(1) O(3) 2252(2) 10845(2) 10042(1) 39(1) C(1) 7173(3) 6291(2) 6908(2) 19(1) C(2) 4726(3) 7147(2) 8610(2) 19(1) C(3) 4451(3) 8279(2) 8644(2) 17(1) C(4) 3513(3) 8539(2) 9181(2) 21(1) C(5) 3290(3) 9623(3) 9292(2) 23(1) C(6) 3994(3) 10493(2) 8871(2) 24(1) C(7) 4907(3) 10257(2) 8335(2) 23(1) C(8) 5165(3) 9148(2) 8188(2) 19(1) C(9) 5746(3) 5576(2) 8351(2) 18(1) C(10) 4911(3) 4694(2) 7856(2) 20(1) C(11) 5229(3) 3615(2) 8034(2) 26(1) C(12) 6310(3) 3437(2) 8688(2) 27(1) C(13) 7084(3) 4319(2) 9191(2) 26(1) C(14) 6829(3) 5417(2) 9036(2) 20(1) C(15) 7666(3) 6397(2) 9590(2) 24(1) C(16) 9240(3) 6311(3) 9861(2) 45(1) C(17) 6976(4) 6538(3) 10383(2) 42(1) C(18) 3687(3) 4916(2) 7158(2) 24(1) C(19) 3270(3) 4001(3) 6457(2) 34(1) C(20) 2351(3) 5092(3) 7531(2) 32(1) C(21) 9521(3) 7942(2) 6248(2) 17(1) C(22) 9367(3) 7128(2) 5605(2) 20(1) C(23) 10542(3) 6679(2) 5411(2) 24(1) C(24) 11875(3) 7049(2) 5864(2) 25(1) C(25) 12054(3) 7849(3) 6509(2) 26(1)
186
C(26) 10874(3) 8296(2) 6706(2) 22(1) C(27) 8728(3) 9898(2) 6924(2) 17(1) C(28) 9079(3) 10091(2) 7806(2) 23(1) C(29) 9822(3) 11104(3) 8136(2) 27(1) C(30) 10219(3) 11932(3) 7585(2) 30(1) C(31) 9865(3) 11764(2) 6710(2) 26(1) C(32) 9125(3) 10749(2) 6373(2) 21(1) C(33) 6848(3) 8648(2) 5483(2) 17(1) C(34) 7401(3) 8937(2) 4731(2) 23(1) C(35) 6491(3) 9056(2) 3973(2) 27(1) C(36) 5027(3) 8892(3) 3950(2) 28(1) C(37) 4473(3) 8598(2) 4685(2) 25(1) C(38) 5371(3) 8484(2) 5446(2) 20(1) C(39) 6418(3) 5791(2) 6150(2) 24(1) C(40) 6680(3) 4757(3) 5859(2) 32(1) C(41) 7701(3) 4213(3) 6333(2) 33(1) C(42) 8489(3) 4702(3) 7070(2) 32(1) C(43) 8261(3) 5743(2) 7356(2) 24(1) _______________________________________________________________________ Table A.4. Bond lengths [Å] and angles [°] for 1a. _______________________________________________________________________ Ni(1)-C(1) 1.893(3) Ni(1)-O(1) 1.9141(19) Ni(1)-N(1) 1.947(2) Ni(1)-P(1) 2.1754(8) P(1)-C(33) 1.823(3) P(1)-C(27) 1.827(3) P(1)-C(21) 1.838(3) N(1)-C(2) 1.298(3) N(1)-C(9) 1.458(3) N(2)-O(2) 1.226(3) N(2)-O(3) 1.232(3) N(2)-C(5) 1.452(4) O(1)-C(8) 1.288(3) C(1)-C(39) 1.385(4) C(1)-C(43) 1.405(4) C(2)-C(3) 1.428(4) C(3)-C(4) 1.394(4) C(3)-C(8) 1.431(4) C(4)-C(5) 1.368(4) C(5)-C(6) 1.396(4) C(6)-C(7) 1.365(4)
C(7)-C(8) 1.418(4) C(9)-C(10) 1.394(4) C(9)-C(14) 1.407(4) C(10)-C(11) 1.395(4) C(10)-C(18) 1.527(4) C(11)-C(12) 1.380(4) C(12)-C(13) 1.378(4) C(13)-C(14) 1.395(4) C(14)-C(15) 1.520(4) C(15)-C(16) 1.516(4) C(15)-C(17) 1.525(4) C(18)-C(19) 1.527(4) C(18)-C(20) 1.531(4) C(21)-C(22) 1.386(4) C(21)-C(26) 1.389(4) C(22)-C(23) 1.388(4) C(23)-C(24) 1.375(4) C(24)-C(25) 1.375(4) C(25)-C(26) 1.394(4) C(27)-C(28) 1.389(4) C(27)-C(32) 1.399(4)
187
C(28)-C(29) 1.381(4) C(29)-C(30) 1.380(4) C(30)-C(31) 1.376(4) C(31)-C(32) 1.386(4) C(33)-C(38) 1.392(4) C(33)-C(34) 1.402(4) C(34)-C(35) 1.382(4) C(35)-C(36) 1.383(4) C(36)-C(37) 1.378(4) C(37)-C(38) 1.380(4) C(39)-C(40) 1.396(4) C(40)-C(41) 1.374(4) C(41)-C(42) 1.365(5) C(42)-C(43) 1.390(4) C(1)-Ni(1)-O(1) 171.64(10) C(1)-Ni(1)-N(1) 92.89(10) O(1)-Ni(1)-N(1) 92.86(8) C(1)-Ni(1)-P(1) 84.86(8) O(1)-Ni(1)-P(1) 89.65(6) N(1)-Ni(1)-P(1) 176.61(7) C(33)-P(1)-C(27) 106.99(12) C(33)-P(1)-C(21) 104.17(13) C(27)-P(1)-C(21) 101.16(13) C(33)-P(1)-Ni(1) 109.30(9) C(27)-P(1)-Ni(1) 113.23(9) C(21)-P(1)-Ni(1) 120.84(9) C(2)-N(1)-C(9) 113.8(2) C(2)-N(1)-Ni(1) 124.33(19) C(9)-N(1)-Ni(1) 121.45(17) O(2)-N(2)-O(3) 122.9(3) O(2)-N(2)-C(5) 118.6(3) O(3)-N(2)-C(5) 118.5(3) C(8)-O(1)-Ni(1) 129.68(18) C(39)-C(1)-C(43) 117.5(3) C(39)-C(1)-Ni(1) 120.6(2) C(43)-C(1)-Ni(1) 121.6(2) N(1)-C(2)-C(3) 127.7(2) C(4)-C(3)-C(2) 117.9(2) C(4)-C(3)-C(8) 119.9(3) C(2)-C(3)-C(8) 122.2(2) C(5)-C(4)-C(3) 120.6(3) C(4)-C(5)-C(6) 120.9(3) C(4)-C(5)-N(2) 118.7(3)
C(6)-C(5)-N(2) 120.4(3) C(7)-C(6)-C(5) 119.6(3) C(6)-C(7)-C(8) 122.0(3) O(1)-C(8)-C(7) 119.9(2) O(1)-C(8)-C(3) 123.1(3) C(7)-C(8)-C(3) 117.0(2) C(10)-C(9)-C(14) 123.0(3) C(10)-C(9)-N(1) 120.0(2) C(14)-C(9)-N(1) 116.9(2) C(9)-C(10)-C(11) 117.4(3) C(9)-C(10)-C(18) 120.5(3) C(11)-C(10)-C(18) 122.1(3) C(12)-C(11)-C(10) 120.8(3) C(13)-C(12)-C(11) 120.7(3) C(12)-C(13)-C(14) 121.1(3) C(13)-C(14)-C(9) 116.9(3) C(13)-C(14)-C(15) 121.6(3) C(9)-C(14)-C(15) 121.4(2) C(16)-C(15)-C(14) 114.6(3) C(16)-C(15)-C(17) 109.6(3) C(14)-C(15)-C(17) 109.7(2) C(10)-C(18)-C(19) 114.0(2) C(10)-C(18)-C(20) 112.0(2) C(19)-C(18)-C(20) 108.6(3) C(22)-C(21)-C(26) 118.9(2) C(22)-C(21)-P(1) 120.3(2) C(26)-C(21)-P(1) 120.8(2) C(21)-C(22)-C(23) 121.0(3) C(24)-C(23)-C(22) 119.4(3) C(23)-C(24)-C(25) 120.8(3) C(24)-C(25)-C(26) 119.8(3) C(21)-C(26)-C(25) 120.2(3) C(28)-C(27)-C(32) 119.1(3) C(28)-C(27)-P(1) 118.8(2) C(32)-C(27)-P(1) 121.7(2) C(29)-C(28)-C(27) 120.7(3) C(30)-C(29)-C(28) 119.6(3) C(31)-C(30)-C(29) 120.7(3) C(30)-C(31)-C(32) 120.1(3) C(31)-C(32)-C(27) 119.9(3) C(38)-C(33)-C(34) 118.4(3) C(38)-C(33)-P(1) 117.5(2) C(34)-C(33)-P(1) 124.1(2) C(35)-C(34)-C(33) 120.3(3)
188
C(34)-C(35)-C(36) 120.3(3) C(37)-C(36)-C(35) 119.8(3) C(36)-C(37)-C(38) 120.4(3) C(37)-C(38)-C(33) 120.7(3) C(1)-C(39)-C(40) 121.4(3)
C(41)-C(40)-C(39) 119.8(3) C(42)-C(41)-C(40) 120.0(3) C(41)-C(42)-C(43) 120.7(3) C(42)-C(43)-C(1) 120.4(3)
_____________________________________________________________ Table A.5. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 2a. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Ni(1) 112(1) 2062(1) 8231(1) 22(1) P(1) 945(2) 1499(1) 7306(1) 23(1) O(1) -1415(4) 1517(2) 7996(3) 27(1) N(1) -534(5) 2515(2) 9188(3) 20(1) N(5) -5201(5) 901(3) 10009(4) 31(1) N(4) 1607(5) 1352(3) 5658(3) 27(1) O(2) -6055(4) 490(2) 9723(3) 37(1) N(3) 2960(5) 726(3) 6880(3) 30(1) C(10) 957(6) 3007(3) 10465(4) 21(1) C(8) -2301(6) 1392(3) 8481(4) 23(1) C(11) 1587(6) 3558(3) 10860(4) 25(1) C(13) 638(6) 4222(3) 9646(4) 26(1) C(31) 1630(6) 3083(3) 7625(4) 28(2) C(1) 1654(6) 2589(3) 8250(4) 24(1) C(23) 2633(6) 1136(3) 7590(4) 28(2) C(7) -3245(6) 888(3) 8228(4) 26(2) C(6) -4176(6) 733(3) 8720(4) 25(1) C(14) -20(6) 3689(3) 9216(4) 20(1) N(2) 637(5) 395(3) 6275(3) 31(1) C(21) 1118(7) 1840(3) 6244(4) 30(2) C(15) -1014(6) 3774(3) 8357(4) 21(1) C(30) 2691(6) 3505(3) 7639(4) 29(2) C(17) -645(6) 4329(3) 7792(4) 28(2) C(3) -2395(6) 1768(3) 9245(4) 23(1) O(3) -5157(5) 1146(3) 10726(3) 48(1)
189
C(9) 154(5) 3081(3) 9636(4) 21(1) C(25) 2946(6) 1114(3) 6086(4) 32(2) C(2) -1557(6) 2309(3) 9514(4) 24(1) C(22) 10(6) 756(3) 6912(4) 28(2) C(5) -4220(6) 1076(3) 9481(4) 24(1) C(24) 2003(6) 192(3) 6667(4) 31(2) C(4) -3369(6) 1593(3) 9733(4) 28(2) C(27) 2851(6) 2519(3) 8871(4) 29(2) C(18) 1157(6) 2363(3) 10955(4) 31(2) C(26) 696(7) 806(3) 5494(4) 30(2) C(12) 1446(6) 4157(3) 10462(4) 30(2) C(29) 3816(7) 3442(4) 8274(5) 40(2) C(28) 3911(6) 2938(4) 8894(4) 34(2) C(16) -2441(6) 3875(3) 8526(4) 30(2) C(20) 417(7) 2375(4) 11736(5) 45(2) C(19) 2636(6) 2203(3) 11284(4) 33(2) Cl(2S) 866(2) 912(1) -455(1) 60(1) Cl(1S) 348(2) 624(1) 1284(1) 69(1) C(1S) 1444(9) 489(5) 533(5) 68(3) _______________________________________________________________________ Table A.6. Bond lengths [Å] and angles [°] for 2a. _______________________________________________________________________ Ni(1)-O(1) 1.888(4) Ni(1)-C(1) 1.893(6) Ni(1)-N(1) 1.964(5) Ni(1)-P(1) 2.1345(18) P(1)-C(21) 1.831(6) P(1)-C(22) 1.839(6) P(1)-C(23) 1.841(6) O(1)-C(8) 1.299(7) N(1)-C(2) 1.304(7) N(1)-C(9) 1.462(7) N(5)-O(3) 1.215(7) N(5)-O(2) 1.231(6) N(5)-C(5) 1.444(7) N(4)-C(26) 1.443(8) N(4)-C(25) 1.477(8) N(4)-C(21) 1.497(8) N(3)-C(24) 1.459(8) N(3)-C(25) 1.466(8) N(3)-C(23) 1.473(7) C(10)-C(11) 1.384(8)
C(10)-C(9) 1.397(8) C(10)-C(18) 1.521(8) C(8)-C(7) 1.413(8) C(8)-C(3) 1.432(8) C(11)-C(12) 1.373(8) C(13)-C(12) 1.382(8) C(13)-C(14) 1.386(8) C(31)-C(30) 1.377(8) C(31)-C(1) 1.401(9) C(1)-C(27) 1.409(8) C(7)-C(6) 1.356(8) C(6)-C(5) 1.383(8) C(14)-C(9) 1.405(8) C(14)-C(15) 1.525(8) N(2)-C(24) 1.464(8) N(2)-C(22) 1.471(7) N(2)-C(26) 1.486(8) C(15)-C(17) 1.524(8) C(15)-C(16) 1.528(8) C(30)-C(29) 1.368(9)
190
C(3)-C(4) 1.397(8) C(3)-C(2) 1.413(8) C(5)-C(4) 1.377(8) C(27)-C(28) 1.369(9) C(18)-C(19) 1.526(8) C(18)-C(20) 1.538(9) C(29)-C(28) 1.405(10) Cl(2S)-C(1S) 1.766(8) Cl(1S)-C(1S) 1.773(8) O(1)-Ni(1)-C(1) 169.7(2) O(1)-Ni(1)-N(1) 92.99(18) C(1)-Ni(1)-N(1) 96.1(2) O(1)-Ni(1)-P(1) 87.68(13) C(1)-Ni(1)-P(1) 83.85(18) N(1)-Ni(1)-P(1) 173.33(15) C(21)-P(1)-C(22) 98.4(3) C(21)-P(1)-C(23) 97.6(3) C(22)-P(1)-C(23) 98.1(3) C(21)-P(1)-Ni(1) 121.0(2) C(22)-P(1)-Ni(1) 115.5(2) C(23)-P(1)-Ni(1) 121.5(2) C(8)-O(1)-Ni(1) 129.3(4) C(2)-N(1)-C(9) 114.6(5) C(2)-N(1)-Ni(1) 122.5(4) C(9)-N(1)-Ni(1) 122.7(4) O(3)-N(5)-O(2) 121.3(5) O(3)-N(5)-C(5) 120.2(5) O(2)-N(5)-C(5) 118.4(5) C(26)-N(4)-C(25) 109.0(5) C(26)-N(4)-C(21) 110.8(5) C(25)-N(4)-C(21) 109.0(5) C(24)-N(3)-C(25) 108.3(5) C(24)-N(3)-C(23) 111.6(5) C(25)-N(3)-C(23) 110.5(5) C(11)-C(10)-C(9) 117.5(6) C(11)-C(10)-C(18) 118.8(5) C(9)-C(10)-C(18) 123.7(6) O(1)-C(8)-C(7) 119.1(5) O(1)-C(8)-C(3) 122.1(5) C(7)-C(8)-C(3) 118.7(5) C(12)-C(11)-C(10) 122.1(6)
C(12)-C(13)-C(14) 121.1(6) C(30)-C(31)-C(1) 122.1(6) C(31)-C(1)-C(27) 116.7(6) C(31)-C(1)-Ni(1) 119.6(5) C(27)-C(1)-Ni(1) 123.7(5) N(3)-C(23)-P(1) 112.3(4) C(6)-C(7)-C(8) 121.2(6) C(7)-C(6)-C(5) 119.9(6) C(13)-C(14)-C(9) 118.0(5) C(13)-C(14)-C(15) 120.7(5) C(9)-C(14)-C(15) 120.9(5) C(24)-N(2)-C(22) 110.8(5) C(24)-N(2)-C(26) 108.9(5) C(22)-N(2)-C(26) 110.4(5) N(4)-C(21)-P(1) 112.9(4) C(17)-C(15)-C(14) 113.4(5) C(17)-C(15)-C(16) 109.7(5) C(14)-C(15)-C(16) 110.9(5) C(29)-C(30)-C(31) 119.7(7) C(4)-C(3)-C(2) 119.1(6) C(4)-C(3)-C(8) 118.2(6) C(2)-C(3)-C(8) 122.7(5) C(10)-C(9)-C(14) 121.7(6) C(10)-C(9)-N(1) 119.8(5) C(14)-C(9)-N(1) 118.5(5) N(3)-C(25)-N(4) 115.1(5) N(1)-C(2)-C(3) 128.1(6) N(2)-C(22)-P(1) 112.5(4) C(4)-C(5)-C(6) 121.1(6) C(4)-C(5)-N(5) 119.4(5) C(6)-C(5)-N(5) 119.5(6) N(3)-C(24)-N(2) 114.6(5) C(5)-C(4)-C(3) 120.7(6) C(28)-C(27)-C(1) 121.7(6) C(10)-C(18)-C(19) 112.7(5) C(10)-C(18)-C(20) 109.9(5) C(19)-C(18)-C(20) 109.3(5) N(4)-C(26)-N(2) 114.7(5) C(11)-C(12)-C(13) 119.6(6) C(30)-C(29)-C(28) 120.4(6) C(27)-C(28)-C(29) 119.3(6) Cl(2S)-C(1S)-Cl(1S) 110.4(5)
_______________________________________________________________________
191
Table A.7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 4a. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pd(1) 6498(1) 6846(1) 7581(1) 23(1) P(1) 7052(3) 7414(2) 8685(2) 21(1) O(1) 7587(7) 8267(6) 6531(4) 23(1) O(2) 7652(8) 11489(6) 2267(5) 36(2) O(3) 6653(8) 9909(7) 2321(5) 42(2) N(1) 6139(7) 6226(6) 6514(5) 16(2) N(2) 8653(8) 8941(7) 9002(5) 23(2) N(3) 8654(8) 6690(7) 10175(5) 28(2) N(4) 6257(8) 8572(7) 10123(5) 26(2) N(5) 7177(8) 10474(7) 2701(5) 28(2) C(1) 5341(11) 5578(9) 8624(6) 28(2) C(2) 6269(9) 6925(8) 5631(6) 21(2) C(3) 6735(9) 8185(8) 5193(6) 21(2) C(4) 6628(9) 8811(8) 4217(6) 22(2) C(5) 7251(10) 9908(9) 3700(6) 26(2) C(6) 7989(10) 10419(9) 4135(7) 32(2) C(7) 8051(11) 9896(9) 5075(7) 30(2) C(8) 7456(10) 8719(8) 5660(6) 22(2) C(9) 5878(9) 4888(8) 6724(6) 20(2) C(10) 7105(10) 3747(8) 6993(6) 20(2) C(11) 6839(10) 2475(9) 7197(6) 26(2) C(12) 5414(10) 2335(8) 7146(6) 26(2) C(13) 4208(10) 3497(8) 6902(6) 23(2) C(14) 4413(9) 4766(8) 6708(5) 20(2) C(15) 3016(9) 5990(8) 6477(6) 22(2) C(16) 2603(11) 6228(9) 5515(7) 32(2) C(17) 1594(9) 5823(8) 7298(7) 25(2) C(18) 8703(10) 3827(9) 7058(7) 29(2) C(19) 9238(14) 2929(12) 8008(9) 57(3) C(20) 9879(11) 3439(12) 6247(8) 42(3) C(21) 5559(9) 8237(8) 9489(6) 23(2) C(22) 8260(10) 8651(9) 8228(6) 26(2) C(23) 8231(10) 6101(8) 9569(6) 26(2) C(24) 9559(10) 7691(9) 9622(6) 29(2) C(25) 7247(10) 7353(9) 10707(6) 27(2) C(26) 7243(10) 9518(9) 9570(6) 27(2) _______________________________________________________________________
192
Table A.8. Bond lengths [Å] and angles [°] for 4a. _______________________________________________________________________ Pd(1)-C(1) 2.024(9) Pd(1)-O(1) 2.094(5) Pd(1)-N(1) 2.097(6) Pd(1)-P(1) 2.199(3) P(1)-C(21) 1.843(9) P(1)-C(23) 1.843(8) P(1)-C(22) 1.844(9) O(1)-C(8) 1.267(10) O(2)-N(5) 1.220(9) O(3)-N(5) 1.230(10) N(1)-C(2) 1.291(10) N(1)-C(9) 1.459(10) N(2)-C(26) 1.469(11) N(2)-C(22) 1.473(11) N(2)-C(24) 1.483(11) N(3)-C(24) 1.467(11) N(3)-C(23) 1.472(11) N(3)-C(25) 1.475(11) N(4)-C(21) 1.473(11) N(4)-C(26) 1.475(11) N(4)-C(25) 1.475(11) N(5)-C(5) 1.441(11) C(2)-C(3) 1.444(12) C(3)-C(4) 1.418(12) C(3)-C(8) 1.426(12) C(4)-C(5) 1.383(12) C(5)-C(6) 1.383(13) C(6)-C(7) 1.354(13) C(7)-C(8) 1.457(12) C(9)-C(14) 1.390(12) C(9)-C(10) 1.401(12) C(10)-C(11) 1.393(12) C(10)-C(18) 1.517(11) C(11)-C(12) 1.378(12) C(12)-C(13) 1.397(12) C(13)-C(14) 1.369(11) C(14)-C(15) 1.535(11) C(15)-C(16) 1.519(12) C(15)-C(17) 1.580(12) C(18)-C(20) 1.524(14) C(18)-C(19) 1.529(14)
C(1)-Pd(1)-O(1) 176.1(3) C(1)-Pd(1)-N(1) 93.5(3) O(1)-Pd(1)-N(1) 88.6(2) C(1)-Pd(1)-P(1) 87.7(3) O(1)-Pd(1)-P(1) 90.44(17) N(1)-Pd(1)-P(1) 175.82(19) C(21)-P(1)-C(23) 98.5(4) C(21)-P(1)-C(22) 98.4(4) C(23)-P(1)-C(22) 99.2(4) C(21)-P(1)-Pd(1) 123.3(3) C(23)-P(1)-Pd(1) 119.0(3) C(22)-P(1)-Pd(1) 114.0(3) C(8)-O(1)-Pd(1) 126.8(5) C(2)-N(1)-C(9) 115.5(6) C(2)-N(1)-Pd(1) 123.4(5) C(9)-N(1)-Pd(1) 120.9(5) C(26)-N(2)-C(22) 111.1(6) C(26)-N(2)-C(24) 109.3(7) C(22)-N(2)-C(24) 110.6(7) C(24)-N(3)-C(23) 111.8(7) C(24)-N(3)-C(25) 108.7(7) C(23)-N(3)-C(25) 110.7(7) C(21)-N(4)-C(26) 110.4(7) C(21)-N(4)-C(25) 111.6(7) C(26)-N(4)-C(25) 107.6(6) O(2)-N(5)-O(3) 122.9(8) O(2)-N(5)-C(5) 118.2(7) O(3)-N(5)-C(5) 118.9(7) N(1)-C(2)-C(3) 128.3(8) C(4)-C(3)-C(8) 119.7(8) C(4)-C(3)-C(2) 116.5(7) C(8)-C(3)-C(2) 123.4(8) C(5)-C(4)-C(3) 121.1(8) C(4)-C(5)-C(6) 120.1(8) C(4)-C(5)-N(5) 119.2(7) C(6)-C(5)-N(5) 120.7(8) C(7)-C(6)-C(5) 120.8(9) C(6)-C(7)-C(8) 122.1(8) O(1)-C(8)-C(3) 125.3(7) O(1)-C(8)-C(7) 118.5(7) C(3)-C(8)-C(7) 116.1(8) C(14)-C(9)-C(10) 121.6(7)
193
C(14)-C(9)-N(1) 120.0(7) C(10)-C(9)-N(1) 118.3(7) C(11)-C(10)-C(9) 117.8(7) C(11)-C(10)-C(18) 118.7(7) C(9)-C(10)-C(18) 123.6(7) C(12)-C(11)-C(10) 121.5(8) C(11)-C(12)-C(13) 118.9(8) C(14)-C(13)-C(12) 121.5(8) C(13)-C(14)-C(9) 118.6(7) C(13)-C(14)-C(15) 118.4(7) C(9)-C(14)-C(15) 123.0(7) C(16)-C(15)-C(14) 111.1(7)
C(16)-C(15)-C(17) 112.9(7) C(14)-C(15)-C(17) 110.5(7) C(10)-C(18)-C(20) 109.7(7) C(10)-C(18)-C(19) 112.1(7) C(20)-C(18)-C(19) 110.4(9) N(4)-C(21)-P(1) 111.9(5) N(2)-C(22)-P(1) 111.4(6) N(3)-C(23)-P(1) 111.5(6) N(3)-C(24)-N(2) 113.7(7) N(3)-C(25)-N(4) 114.9(7) N(2)-C(26)-N(4) 114.7(7)
_______________________________________________________________________ Table A.9. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 4b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pd(1) 7041(1) 1818(1) 3429(1) 13(1) P(1) 8045(1) 2556(1) 2919(1) 14(1) O(1) 6410(2) 1343(1) 2713(1) 16(1) O(2) 5820(2) 1038(1) 1703(1) 24(1) N(1) 5954(2) 1216(2) 3917(1) 13(1) N(2) 8612(2) 3028(2) 1866(1) 19(1) N(3) 9988(2) 3193(2) 2613(1) 15(1) N(4) 8361(2) 3969(2) 2587(1) 18(1) C(1) 7690(3) 2328(2) 4110(2) 22(1) C(2) 5146(3) 861(2) 3705(2) 16(1) C(3) 4865(3) 746(2) 3132(2) 14(1) C(4) 3849(3) 409(2) 3021(2) 19(1) C(5) 3485(3) 290(2) 2492(2) 24(1) C(6) 4133(3) 493(2) 2036(2) 22(1) C(7) 5125(3) 811(2) 2120(2) 18(1) C(8) 5516(3) 984(2) 2673(2) 15(1) C(9) 5976(3) 1275(2) 4525(2) 17(1) C(10) 6642(3) 794(2) 4828(2) 17(1) C(11) 6697(3) 894(2) 5410(2) 23(1) C(12) 6132(3) 1443(2) 5673(2) 24(1) C(13) 5499(3) 1911(2) 5361(2) 23(1) C(14) 5404(3) 1840(2) 4778(2) 18(1)
194
C(15) 4703(3) 2354(2) 4434(2) 22(1) C(16) 4784(4) 3140(2) 4632(2) 32(1) C(17) 3509(3) 2113(2) 4426(2) 28(1) C(18) 7254(3) 196(2) 4537(2) 22(1) C(19) 8350(3) 25(2) 4804(2) 37(1) C(20) 6554(4) -483(2) 4505(2) 36(1) C(21) 7696(3) 3523(2) 2963(2) 18(1) C(22) 7977(3) 2454(2) 2148(1) 20(1) C(23) 9539(3) 2646(2) 2999(2) 15(1) C(24) 9758(3) 2994(2) 2028(2) 20(1) C(25) 9517(3) 3904(2) 2725(2) 19(1) C(26) 8203(3) 3744(2) 2000(2) 22(1) C(27) 5438(4) 975(2) 1138(2) 41(1) Table A.10. Bond lengths [Å] and angles [°] for 4b. _______________________________________________________________________ Pd(1)-C(1) 2.036(4) Pd(1)-O(1) 2.068(2) Pd(1)-N(1) 2.087(3) Pd(1)-P(1) 2.1995(12) P(1)-C(21) 1.839(4) P(1)-C(23) 1.847(4) P(1)-C(22) 1.848(4) O(1)-C(8) 1.283(4) O(2)-C(7) 1.373(4) O(2)-C(27) 1.429(4) N(1)-C(2) 1.290(4) N(1)-C(9) 1.454(5) N(2)-C(26) 1.448(5) N(2)-C(24) 1.457(5) N(2)-C(22) 1.477(5) N(3)-C(25) 1.459(4) N(3)-C(24) 1.467(5) N(3)-C(23) 1.472(4) N(4)-C(21) 1.463(5) N(4)-C(25) 1.459(5) N(4)-C(26) 1.470(5) C(2)-C(3) 1.424(5) C(3)-C(4) 1.417(5) C(3)-C(8) 1.421(5) C(4)-C(5) 1.354(5) C(5)-C(6) 1.396(6) C(6)-C(7) 1.364(5)
C(7)-C(8) 1.438(5) C(9)-C(14) 1.392(5) C(9)-C(10) 1.405(5) C(10)-C(11) 1.400(5) C(10)-C(18) 1.504(5) C(11)-C(12) 1.377(5) C(12)-C(13) 1.378(5) C(13)-C(14) 1.397(5) C(14)-C(15) 1.519(5) C(15)-C(16) 1.529(5) C(15)-C(17) 1.529(5) C(18)-C(19) 1.518(5) C(18)-C(20) 1.521(5) C(1)-Pd(1)-O(1) 177.13(13) C(1)-Pd(1)-N(1) 92.98(13) O(1)-Pd(1)-N(1) 89.67(11) C(1)-Pd(1)-P(1) 86.26(11) O(1)-Pd(1)-P(1) 90.98(8) N(1)-Pd(1)-P(1) 173.27(8) C(21)-P(1)-C(23) 97.88(16) C(21)-P(1)-C(22) 98.28(17) C(23)-P(1)-C(22) 98.98(17) C(21)-P(1)-Pd(1) 116.10(12) C(23)-P(1)-Pd(1) 123.60(12) C(22)-P(1)-Pd(1) 117.36(13) C(8)-O(1)-Pd(1) 126.8(2)
195
C(7)-O(2)-C(27) 116.9(3) C(2)-N(1)-C(9) 116.2(3) C(2)-N(1)-Pd(1) 122.9(3) C(9)-N(1)-Pd(1) 120.2(2) C(26)-N(2)-C(24) 108.3(3) C(26)-N(2)-C(22) 111.9(3) C(24)-N(2)-C(22) 110.8(3) C(25)-N(3)-C(24) 108.8(3) C(25)-N(3)-C(23) 110.8(3) C(24)-N(3)-C(23) 110.5(3) C(21)-N(4)-C(25) 110.9(3) C(21)-N(4)-C(26) 110.5(3) C(25)-N(4)-C(26) 108.5(3) N(1)-C(2)-C(3) 129.4(4) C(4)-C(3)-C(8) 119.0(3) C(4)-C(3)-C(2) 117.1(3) C(8)-C(3)-C(2) 123.8(3) C(5)-C(4)-C(3) 122.2(4) C(4)-C(5)-C(6) 119.5(4) C(7)-C(6)-C(5) 120.6(4) C(6)-C(7)-O(2) 125.3(3) C(6)-C(7)-C(8) 121.7(4) O(2)-C(7)-C(8) 112.9(3) O(1)-C(8)-C(3) 125.5(3) O(1)-C(8)-C(7) 117.7(3)
C(3)-C(8)-C(7) 116.7(3) C(14)-C(9)-C(10) 122.9(3) C(14)-C(9)-N(1) 118.6(3) C(10)-C(9)-N(1) 118.3(3) C(11)-C(10)-C(9) 116.9(3) C(11)-C(10)-C(18) 121.9(3) C(9)-C(10)-C(18) 121.2(3) C(12)-C(11)-C(10) 121.5(4) C(11)-C(12)-C(13) 119.9(4) C(12)-C(13)-C(14) 121.6(4) C(9)-C(14)-C(13) 117.2(3) C(9)-C(14)-C(15) 121.2(3) C(13)-C(14)-C(15) 121.6(3) C(14)-C(15)-C(16) 112.9(3) C(14)-C(15)-C(17) 111.6(3) C(16)-C(15)-C(17) 110.0(3) C(10)-C(18)-C(19) 113.7(3) C(10)-C(18)-C(20) 110.3(3) C(19)-C(18)-C(20) 110.4(3) N(4)-C(21)-P(1) 112.5(2) N(2)-C(22)-P(1) 110.8(2) N(3)-C(23)-P(1) 111.6(2) N(2)-C(24)-N(3) 115.2(3) N(3)-C(25)-N(4) 114.6(3) N(2)-C(26)-N(4) 114.9(3)
_______________________________________________________________________ Table A.11. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 3b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Ni(1) 8752(1) 6365(1) 3064(1) 34(1) P(1) 8311(2) 6964(1) 4161(2) 32(1) N(1) 9139(6) 5800(2) 2091(5) 30(2) N(2) 9224(5) 7668(2) 6230(5) 30(2) N(3) 7002(6) 7265(3) 5575(6) 42(2) N(4) 7402(6) 8038(3) 4342(6) 39(2) O(1) 10498(5) 6606(2) 3935(4) 34(1) O(2) 12711(5) 7124(2) 5318(5) 38(1) C(1) 6904(7) 6209(3) 2236(8) 50(2)
196
C(2) 10288(7) 5749(3) 2105(7) 34(2) C(3) 11448(7) 6061(3) 2843(7) 29(2) C(4) 12589(7) 5930(3) 2664(7) 37(2) C(5) 13753(7) 6191(3) 3392(7) 36(2) C(6) 13811(7) 6595(3) 4291(7) 34(2) C(7) 12750(7) 6738(3) 4479(7) 29(2) C(8) 11498(7) 6457(3) 3719(7) 31(2) C(9) 8150(7) 5424(3) 1218(7) 30(2) C(10) 7897(7) 4918(3) 1721(8) 36(2) C(11) 6910(8) 4568(3) 859(9) 42(2) C(12) 6237(8) 4707(3) -361(8) 43(2) C(13) 6523(8) 5198(3) -813(8) 44(2) C(14) 7491(7) 5566(3) -24(8) 35(2) C(15) 7827(8) 6106(3) -522(8) 47(2) C(16) 8697(9) 5974(4) -1173(8) 67(3) C(17) 6613(9) 6435(3) -1374(8) 66(3) C(18) 8614(8) 4773(3) 3086(8) 40(2) C(19) 9814(8) 4414(3) 3334(8) 62(3) C(20) 7770(9) 4472(4) 3618(9) 73(3) C(21) 7601(8) 7652(3) 3456(7) 46(2) C(22) 9653(7) 7234(3) 5574(7) 34(2) C(23) 7193(7) 6780(3) 4841(7) 40(2) C(24) 8258(7) 7423(3) 6591(7) 39(2) C(25) 6516(8) 7775(3) 4791(8) 49(2) C(26) 8623(7) 8165(3) 5420(7) 36(2) C(27) 13883(7) 7417(4) 6034(8) 47(2) Cl(1S) 6236(3) 5328(1) 5549(4) 137(2) C(1S) 4810(20) 5107(8) 5468(14) 172(7) _______________________________________________________________________ Table A.12. Bond lengths [Å] and angles [°] 3b. _______________________________________________________________________ Ni(1)-O(1) 1.881(5) Ni(1)-C(1) 1.926(8) Ni(1)-N(1) 1.931(6) Ni(1)-P(1) 2.119(2) P(1)-C(22) 1.819(7) P(1)-C(23) 1.829(7) P(1)-C(21) 1.834(8) N(1)-C(2) 1.304(8) N(1)-C(9) 1.449(8) N(2)-C(24) 1.459(8) N(2)-C(26) 1.476(8)
N(2)-C(22) 1.486(8) N(3)-C(24) 1.459(9) N(3)-C(25) 1.467(9) N(3)-C(23) 1.503(9) N(4)-C(26) 1.449(9) N(4)-C(25) 1.466(9) N(4)-C(21) 1.479(9) O(1)-C(8) 1.317(8) O(2)-C(7) 1.361(8) O(2)-C(27) 1.407(8) C(2)-C(3) 1.426(10)
197
C(3)-C(8) 1.377(9) C(3)-C(4) 1.436(9) C(4)-C(5) 1.370(9) C(5)-C(6) 1.406(9) C(6)-C(7) 1.360(9) C(7)-C(8) 1.467(9) C(9)-C(14) 1.372(10) C(9)-C(10) 1.413(9) C(10)-C(11) 1.406(10) C(10)-C(18) 1.501(10) C(11)-C(12) 1.350(10) C(12)-C(13) 1.368(10) C(13)-C(14) 1.391(10) C(14)-C(15) 1.515(10) C(15)-C(17) 1.517(11) C(15)-C(16) 1.530(11) C(18)-C(19) 1.518(10) C(18)-C(20) 1.532(10) Cl(1S)-C(1S)#1 1.63(2) Cl(1S)-C(1S) 1.67(2) C(1S)-C(1S)#1 1.45(3) C(1S)-Cl(1S)#1 1.63(2) O(1)-Ni(1)-C(1) 172.7(3) O(1)-Ni(1)-N(1) 94.2(2) C(1)-Ni(1)-N(1) 92.7(3) O(1)-Ni(1)-P(1) 86.50(15) C(1)-Ni(1)-P(1) 86.7(2) N(1)-Ni(1)-P(1) 178.20(18) C(22)-P(1)-C(23) 98.0(3) C(22)-P(1)-C(21) 98.0(4) C(23)-P(1)-C(21) 99.0(4) C(22)-P(1)-Ni(1) 118.0(2) C(23)-P(1)-Ni(1) 120.8(3) C(21)-P(1)-Ni(1) 118.5(3) C(2)-N(1)-C(9) 114.4(6) C(2)-N(1)-Ni(1) 123.0(5) C(9)-N(1)-Ni(1) 122.5(5) C(24)-N(2)-C(26) 108.0(5) C(24)-N(2)-C(22) 110.2(5) C(26)-N(2)-C(22) 111.3(5) C(24)-N(3)-C(25) 106.2(6) C(24)-N(3)-C(23) 109.6(6) C(25)-N(3)-C(23) 111.0(6)
C(26)-N(4)-C(25) 108.1(6) C(26)-N(4)-C(21) 111.7(6) C(25)-N(4)-C(21) 110.1(6) C(8)-O(1)-Ni(1) 127.3(4) C(7)-O(2)-C(27) 116.2(6) N(1)-C(2)-C(3) 127.8(7) C(8)-C(3)-C(2) 122.2(7) C(8)-C(3)-C(4) 120.9(7) C(2)-C(3)-C(4) 116.8(6) C(5)-C(4)-C(3) 119.8(7) C(4)-C(5)-C(6) 119.5(7) C(7)-C(6)-C(5) 122.7(7) C(6)-C(7)-O(2) 126.8(7) C(6)-C(7)-C(8) 118.6(7) O(2)-C(7)-C(8) 114.6(6) O(1)-C(8)-C(3) 124.9(7) O(1)-C(8)-C(7) 116.6(6) C(3)-C(8)-C(7) 118.5(7) C(14)-C(9)-C(10) 122.9(7) C(14)-C(9)-N(1) 120.6(6) C(10)-C(9)-N(1) 116.5(7) C(11)-C(10)-C(9) 115.2(7) C(11)-C(10)-C(18) 122.6(7) C(9)-C(10)-C(18) 122.2(7) C(12)-C(11)-C(10) 122.7(8) C(11)-C(12)-C(13) 120.2(8) C(12)-C(13)-C(14) 120.8(8) C(9)-C(14)-C(13) 118.2(7) C(9)-C(14)-C(15) 120.7(7) C(13)-C(14)-C(15) 121.1(7) C(14)-C(15)-C(17) 112.0(7) C(14)-C(15)-C(16) 110.9(7) C(17)-C(15)-C(16) 111.5(7) C(10)-C(18)-C(19) 110.7(7) C(10)-C(18)-C(20) 114.0(7) C(19)-C(18)-C(20) 109.7(7) N(4)-C(21)-P(1) 112.8(5) N(2)-C(22)-P(1) 112.8(5) N(3)-C(23)-P(1) 112.5(5) N(2)-C(24)-N(3) 116.6(6) N(4)-C(25)-N(3) 116.4(6) N(4)-C(26)-N(2) 113.9(6) C(1S)#1-Cl(1S)-C(1S) 52.3(9) C(1S)#1-C(1S)-Cl(1S)#1 65.3(15)
198
C(1S)#1-C(1S)-Cl(1S) 62.4(16) Cl(1S)#1-C(1S)-Cl(1S) 127.7(8) Table A.13. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 3d. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Ni(1) 7596(1) 1265(1) 9402(1) 25(1) Cl(1) 11427(1) 1483(1) 11499(1) 43(1) Cl(2) 11973(1) 4590(1) 10116(1) 54(1) P(1) 7776(1) 318(1) 10451(1) 25(1) N(1) 7479(3) 2232(2) 8579(2) 21(1) N(2) 9208(3) -800(2) 11711(3) 31(1) N(3) 7097(3) -1056(2) 11313(3) 33(1) N(4) 7995(3) 186(2) 12298(3) 31(1) O(1) 9155(2) 1522(2) 10105(2) 28(1) C(1) 6031(4) 874(3) 8839(3) 36(1) C(2) 8250(4) 2835(3) 8723(3) 26(1) C(3) 9346(4) 2885(3) 9441(3) 25(1) C(4) 10037(4) 3616(3) 9460(4) 31(1) C(5) 11120(4) 3678(3) 10083(4) 32(1) C(6) 11555(4) 3017(3) 10710(3) 29(1) C(7) 10890(4) 2306(3) 10702(3) 29(1) C(8) 9758(4) 2207(3) 10080(3) 22(1) C(9) 6546(4) 2334(3) 7719(3) 24(1) C(10) 6667(4) 1925(3) 6942(3) 25(1) C(11) 5775(4) 2029(3) 6126(4) 35(1) C(12) 4806(4) 2526(3) 6071(4) 35(1) C(13) 4698(4) 2920(3) 6843(3) 31(1) C(14) 5563(4) 2824(3) 7696(3) 26(1) C(15) 5416(4) 3259(3) 8543(3) 28(1) C(16) 5735(4) 4212(3) 8554(4) 40(1) C(17) 4199(4) 3147(3) 8616(4) 34(1) C(18) 7711(4) 1376(3) 6972(4) 32(1) C(19) 8202(4) 1593(3) 6192(4) 38(1) C(20) 7415(5) 414(3) 6962(4) 50(2) C(21) 6769(4) -582(3) 10435(3) 31(1) C(22) 7782(4) 817(3) 11543(3) 28(1) C(23) 9140(4) -292(3) 10880(3) 28(1) C(24) 9117(4) -242(3) 12460(3) 32(1)
199
C(25) 8263(4) -1433(3) 11515(4) 38(1) C(26) 7086(4) -483(3) 12071(4) 34(1) _______________________________________________________________________ Table A.14. Bond lengths [Å] and angles [°] for A.14. _______________________________________________________________________ Ni(1)-O(1) 1.907(3) Ni(1)-C(1) 1.923(4) Ni(1)-N(1) 1.936(4) Ni(1)-P(1) 2.1381(14) Cl(1)-C(7) 1.746(5) Cl(2)-C(5) 1.742(5) P(1)-C(22) 1.843(5) P(1)-C(23) 1.841(4) P(1)-C(21) 1.849(4) N(1)-C(2) 1.293(5) N(1)-C(9) 1.456(5) N(2)-C(24) 1.469(6) N(2)-C(25) 1.467(6) N(2)-C(23) 1.479(5) N(3)-C(26) 1.467(6) N(3)-C(25) 1.473(6) N(3)-C(21) 1.476(6) N(4)-C(24) 1.466(5) N(4)-C(26) 1.475(6) N(4)-C(22) 1.475(6) O(1)-C(8) 1.296(5) C(2)-C(3) 1.441(6) C(3)-C(4) 1.404(6) C(3)-C(8) 1.417(6) C(4)-C(5) 1.367(7) C(5)-C(6) 1.391(6) C(6)-C(7) 1.364(6) C(7)-C(8) 1.417(6) C(9)-C(10) 1.398(6) C(9)-C(14) 1.405(6) C(10)-C(11) 1.386(6) C(10)-C(18) 1.516(6) C(11)-C(12) 1.387(6) C(12)-C(13) 1.375(6) C(13)-C(14) 1.407(6) C(14)-C(15) 1.523(6) C(15)-C(17) 1.527(6)
C(15)-C(16) 1.525(6) C(18)-C(20) 1.531(6) C(18)-C(19) 1.532(6) O(1)-Ni(1)-C(1) 171.03(17) O(1)-Ni(1)-N(1) 93.71(13) C(1)-Ni(1)-N(1) 95.17(17) O(1)-Ni(1)-P(1) 82.38(10) C(1)-Ni(1)-P(1) 88.65(15) N(1)-Ni(1)-P(1) 172.58(12) C(22)-P(1)-C(23) 98.2(2) C(22)-P(1)-C(21) 98.2(2) C(23)-P(1)-C(21) 97.8(2) C(22)-P(1)-Ni(1) 111.53(16) C(23)-P(1)-Ni(1) 119.37(15) C(21)-P(1)-Ni(1) 126.53(17) C(2)-N(1)-C(9) 113.2(4) C(2)-N(1)-Ni(1) 123.2(3) C(9)-N(1)-Ni(1) 123.6(3) C(24)-N(2)-C(25) 108.0(4) C(24)-N(2)-C(23) 111.3(4) C(25)-N(2)-C(23) 110.4(4) C(26)-N(3)-C(25) 108.6(4) C(26)-N(3)-C(21) 110.9(4) C(25)-N(3)-C(21) 110.9(4) C(24)-N(4)-C(26) 108.1(3) C(24)-N(4)-C(22) 110.9(3) C(26)-N(4)-C(22) 110.2(4) C(8)-O(1)-Ni(1) 128.7(3) N(1)-C(2)-C(3) 128.0(4) C(4)-C(3)-C(8) 120.3(4) C(4)-C(3)-C(2) 117.5(4) C(8)-C(3)-C(2) 122.1(4) C(5)-C(4)-C(3) 120.6(5) C(4)-C(5)-C(6) 120.5(4) C(4)-C(5)-Cl(2) 120.8(4) C(6)-C(5)-Cl(2) 118.8(4)
200
C(7)-C(6)-C(5) 119.5(4) C(6)-C(7)-C(8) 122.8(4) C(6)-C(7)-Cl(1) 119.5(4) C(8)-C(7)-Cl(1) 117.6(3) O(1)-C(8)-C(7) 120.5(4) O(1)-C(8)-C(3) 123.1(4) C(7)-C(8)-C(3) 116.3(4) C(10)-C(9)-C(14) 122.5(4) C(10)-C(9)-N(1) 117.7(4) C(14)-C(9)-N(1) 119.8(4) C(11)-C(10)-C(9) 117.2(4) C(11)-C(10)-C(18) 120.2(4) C(9)-C(10)-C(18) 122.6(4) C(12)-C(11)-C(10) 121.9(5) C(13)-C(12)-C(11) 120.1(5) C(12)-C(13)-C(14) 120.6(4)
C(13)-C(14)-C(9) 117.6(4) C(13)-C(14)-C(15) 119.6(4) C(9)-C(14)-C(15) 122.8(4) C(14)-C(15)-C(17) 112.8(4) C(14)-C(15)-C(16) 109.9(4) C(17)-C(15)-C(16) 110.9(4) C(10)-C(18)-C(20) 110.8(4) C(10)-C(18)-C(19) 112.2(4) C(20)-C(18)-C(19) 110.7(4) N(3)-C(21)-P(1) 111.9(3) N(4)-C(22)-P(1) 112.8(3) N(2)-C(23)-P(1) 112.5(3) N(4)-C(24)-N(2) 115.3(4) N(2)-C(25)-N(3) 114.6(4) N(3)-C(26)-N(4) 114.9(4)
_______________________________________________________________________ Table A.15. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 4c. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pd(1) 6332(1) 7516(1) -24(1) 16(1) P(1) 4600(1) 6700(1) -1803(1) 17(1) O(1) 6279(3) 5764(2) -404(2) 18(1) N(1) 7996(3) 8214(2) 1613(2) 14(1) N(2) 3954(3) 6116(2) -4166(2) 20(1) N(3) 1944(3) 6380(2) -3344(2) 17(1) N(4) 2641(3) 4525(2) -3797(2) 18(1) C(1) 6273(4) 9191(3) 292(3) 28(1) C(2) 8715(4) 7562(3) 1863(3) 15(1) C(3) 8549(4) 6299(3) 1156(3) 13(1) C(4) 9654(4) 5852(3) 1583(3) 13(1) C(5) 9417(4) 4569(3) 972(3) 16(1) C(6) 8097(4) 3769(3) -36(3) 18(1) C(7) 7075(4) 4182(3) -446(3) 17(1) C(8) 7287(4) 5477(3) 105(3) 14(1) C(9) 8425(4) 9444(3) 2611(3) 15(1) C(10) 9612(4) 10392(3) 2778(3) 17(1) C(11) 10080(4) 11527(3) 3805(3) 21(1)
201
C(12) 9379(4) 11731(3) 4627(3) 22(1) C(13) 8154(4) 10810(3) 4412(3) 21(1) C(14) 7634(4) 9645(3) 3397(3) 18(1) C(15) 6272(4) 8656(3) 3173(3) 23(1) C(16) 6508(4) 8297(3) 4123(3) 40(1) C(17) 4917(4) 9054(3) 3059(3) 35(1) C(18) 10371(4) 10182(3) 1860(3) 21(1) C(19) 10637(4) 11232(3) 1594(3) 30(1) C(20) 11815(4) 9981(3) 2251(3) 35(1) C(21) 2917(4) 7107(3) -2077(3) 20(1) C(22) 3706(4) 5021(3) -2586(3) 17(1) C(23) 5171(4) 6808(3) -2993(3) 19(1) C(24) 3385(4) 4802(3) -4539(3) 21(1) C(25) 2723(4) 6578(3) -4101(3) 21(1) C(26) 1467(4) 5057(3) -3751(3) 21(1) C(27) 10994(4) 6611(3) 2561(3) 16(1) C(28) 12006(4) 6159(3) 2952(3) 22(1) C(29) 11744(4) 4901(3) 2355(3) 22(1) C(30) 10481(4) 4126(3) 1375(3) 21(1) Table A.16. Bond lengths [Å] and angles [°] for 4c. _______________________________________________________________________ Pd(1)-C(1) 2.026(3) Pd(1)-O(1) 2.072(2) Pd(1)-N(1) 2.074(3) Pd(1)-P(1) 2.2080(10) P(1)-C(22) 1.834(3) P(1)-C(23) 1.840(3) P(1)-C(21) 1.845(4) O(1)-C(8) 1.283(4) N(1)-C(2) 1.303(4) N(1)-C(9) 1.444(4) N(2)-C(25) 1.460(4) N(2)-C(23) 1.470(4) N(2)-C(24) 1.473(4) N(3)-C(25) 1.465(4) N(3)-C(21) 1.469(4) N(3)-C(26) 1.470(4) N(4)-C(26) 1.461(4) N(4)-C(24) 1.466(4) N(4)-C(22) 1.470(4) C(2)-C(3) 1.430(4) C(3)-C(8) 1.413(4)
C(3)-C(4) 1.451(5) C(4)-C(27) 1.403(4) C(4)-C(5) 1.425(4) C(5)-C(30) 1.404(5) C(5)-C(6) 1.414(5) C(6)-C(7) 1.348(5) C(7)-C(8) 1.443(4) C(9)-C(10) 1.397(4) C(9)-C(14) 1.404(4) C(10)-C(11) 1.383(4) C(10)-C(18) 1.521(4) C(11)-C(12) 1.377(4) C(12)-C(13) 1.374(4) C(13)-C(14) 1.392(4) C(14)-C(15) 1.510(4) C(15)-C(16) 1.510(5) C(15)-C(17) 1.525(5) C(18)-C(20) 1.515(5) C(18)-C(19) 1.527(4) C(27)-C(28) 1.369(5) C(28)-C(29) 1.391(4)
202
C(29)-C(30) 1.363(5) C(1)-Pd(1)-O(1) 177.06(13) C(1)-Pd(1)-N(1) 94.15(13) O(1)-Pd(1)-N(1) 88.47(10) C(1)-Pd(1)-P(1) 88.23(11) O(1)-Pd(1)-P(1) 89.18(7) N(1)-Pd(1)-P(1) 177.27(8) C(22)-P(1)-C(23) 98.02(15) C(22)-P(1)-C(21) 98.75(16) C(23)-P(1)-C(21) 97.61(15) C(22)-P(1)-Pd(1) 114.87(11) C(23)-P(1)-Pd(1) 118.21(11) C(21)-P(1)-Pd(1) 124.54(11) C(8)-O(1)-Pd(1) 127.2(2) C(2)-N(1)-C(9) 113.1(3) C(2)-N(1)-Pd(1) 123.1(2) C(9)-N(1)-Pd(1) 123.8(2) C(25)-N(2)-C(23) 110.3(3) C(25)-N(2)-C(24) 108.0(3) C(23)-N(2)-C(24) 110.4(3) C(25)-N(3)-C(21) 111.0(3) C(25)-N(3)-C(26) 107.5(3) C(21)-N(3)-C(26) 110.6(3) C(26)-N(4)-C(24) 107.9(3) C(26)-N(4)-C(22) 110.9(3) C(24)-N(4)-C(22) 111.0(3) N(1)-C(2)-C(3) 130.2(3) C(8)-C(3)-C(2) 121.1(3) C(8)-C(3)-C(4) 120.2(3) C(2)-C(3)-C(4) 118.6(3) C(27)-C(4)-C(5) 116.3(3) C(27)-C(4)-C(3) 124.2(3) C(5)-C(4)-C(3) 119.5(3) C(30)-C(5)-C(6) 121.6(3)
C(30)-C(5)-C(4) 120.0(3) C(6)-C(5)-C(4) 118.4(3) C(7)-C(6)-C(5) 122.4(3) C(6)-C(7)-C(8) 121.7(3) O(1)-C(8)-C(3) 126.3(3) O(1)-C(8)-C(7) 116.0(3) C(3)-C(8)-C(7) 117.7(3) C(10)-C(9)-C(14) 121.9(3) C(10)-C(9)-N(1) 119.7(3) C(14)-C(9)-N(1) 118.4(3) C(11)-C(10)-C(9) 117.8(3) C(11)-C(10)-C(18) 121.0(3) C(9)-C(10)-C(18) 121.1(3) C(12)-C(11)-C(10) 121.4(3) C(13)-C(12)-C(11) 120.0(3) C(12)-C(13)-C(14) 121.4(3) C(13)-C(14)-C(9) 117.3(3) C(13)-C(14)-C(15) 120.3(3) C(9)-C(14)-C(15) 122.4(3) C(14)-C(15)-C(16) 112.3(3) C(14)-C(15)-C(17) 110.7(3) C(16)-C(15)-C(17) 110.9(3) C(20)-C(18)-C(10) 111.4(3) C(20)-C(18)-C(19) 110.6(3) C(10)-C(18)-C(19) 111.9(3) N(3)-C(21)-P(1) 112.1(2) N(4)-C(22)-P(1) 112.3(2) N(2)-C(23)-P(1) 113.0(2) N(4)-C(24)-N(2) 115.0(3) N(2)-C(25)-N(3) 115.6(3) N(4)-C(26)-N(3) 115.7(3) C(28)-C(27)-C(4) 122.7(3) C(27)-C(28)-C(29) 120.0(4) C(30)-C(29)-C(28) 119.6(4) C(29)-C(30)-C(5) 121.3(3)
_______________________________________________________________________
203
Table A.17. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 4d. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pd(1) 9662(1) 900(1) 1676(1) 24(1) P(1) 11084(2) -429(2) 1659(2) 25(1) O(1) 9609(6) 640(5) 2634(4) 35(2) N(1) 8404(7) 2242(6) 1771(5) 22(2) N(2) 13291(8) -1087(6) 2231(5) 35(3) N(3) 12892(9) -1770(7) 1153(5) 45(3) N(4) 11739(7) -2547(6) 2031(5) 33(3) Cl(1) 10202(2) -150(2) 3875(1) 35(1) Cl(2) 7154(3) 3131(2) 4629(2) 53(1) C(1) 9776(10) 1065(8) 725(5) 36(3) C(2) 8042(8) 2605(8) 2296(6) 26(3) C(3) 8301(8) 2188(7) 2926(5) 22(3) C(4) 7755(9) 2758(8) 3428(6) 31(3) C(5) 7926(10) 2438(9) 4035(6) 35(3) C(6) 8688(10) 1537(8) 4178(6) 35(3) C(7) 9242(8) 949(7) 3708(5) 22(2) C(8) 9063(9) 1230(8) 3061(6) 28(3) C(9) 8019(8) 2860(7) 1221(5) 24(3) C(10) 8702(9) 3818(7) 1052(5) 26(3) C(11) 8341(9) 4345(8) 508(5) 26(3) C(12) 7385(10) 3955(7) 138(6) 36(3) C(13) 6732(9) 3005(8) 302(6) 31(3) C(14) 7040(8) 2449(7) 840(5) 26(3) C(15) 6307(11) 1423(8) 1057(6) 38(4) C(16) 5282(12) 1746(10) 1494(8) 58(4) C(17) 5811(12) 752(9) 505(7) 53(4) C(18) 9786(8) 4251(7) 1453(5) 25(3) C(19) 10965(10) 4431(9) 1065(7) 42(4) C(20) 9405(10) 5306(8) 1787(6) 40(4) C(21) 11961(11) -927(9) 979(6) 46(4) C(22) 10657(9) -1783(7) 1982(6) 38(3) C(23) 12395(9) -155(8) 2207(6) 39(4) C(24) 12688(10) -2091(8) 2465(6) 39(4) C(25) 13799(10) -1320(8) 1627(7) 41(4) C(26) 12288(10) -2743(7) 1440(6) 34(3) _______________________________________________________________________
204
Table A.18. Bond lengths [Å] and angles [°] for 4d. _______________________________________________________________________ Pd(1)-C(1) 2.045(12) Pd(1)-O(1) 2.068(9) Pd(1)-N(1) 2.117(8) Pd(1)-P(1) 2.211(3) P(1)-C(22) 1.833(10) P(1)-C(21) 1.841(14) P(1)-C(23) 1.841(9) O(1)-C(8) 1.302(14) N(1)-C(2) 1.269(14) N(1)-C(9) 1.443(12) N(2)-C(25) 1.436(16) N(2)-C(24) 1.464(14) N(2)-C(23) 1.477(11) N(3)-C(21) 1.466(12) N(3)-C(26) 1.478(15) N(3)-C(25) 1.492(13) N(4)-C(26) 1.421(15) N(4)-C(24) 1.469(12) N(4)-C(22) 1.482(11) Cl(1)-C(7) 1.711(9) Cl(2)-C(5) 1.740(13) C(2)-C(3) 1.457(15) C(3)-C(4) 1.408(15) C(3)-C(8) 1.440(12) C(4)-C(5) 1.361(16) C(5)-C(6) 1.389(14) C(6)-C(7) 1.372(16) C(7)-C(8) 1.431(16) C(9)-C(14) 1.406(12) C(9)-C(10) 1.417(13) C(10)-C(11) 1.373(13) C(10)-C(18) 1.520(12) C(11)-C(12) 1.364(12) C(12)-C(13) 1.390(15) C(13)-C(14) 1.363(14) C(14)-C(15) 1.541(15) C(15)-C(16) 1.505(19) C(15)-C(17) 1.516(14) C(18)-C(20) 1.518(14) C(18)-C(19) 1.537(17) C(1)-Pd(1)-O(1) 176.4(3)
C(1)-Pd(1)-N(1) 94.0(4) O(1)-Pd(1)-N(1) 89.6(3) C(1)-Pd(1)-P(1) 90.0(3) O(1)-Pd(1)-P(1) 86.4(2) N(1)-Pd(1)-P(1) 174.2(2) C(22)-P(1)-C(21) 98.0(6) C(22)-P(1)-C(23) 96.5(5) C(21)-P(1)-C(23) 99.5(5) C(22)-P(1)-Pd(1) 117.6(4) C(21)-P(1)-Pd(1) 127.7(4) C(23)-P(1)-Pd(1) 112.1(3) C(8)-O(1)-Pd(1) 128.9(6) C(2)-N(1)-C(9) 116.8(8) C(2)-N(1)-Pd(1) 123.5(7) C(9)-N(1)-Pd(1) 119.4(7) C(25)-N(2)-C(24) 108.7(9) C(25)-N(2)-C(23) 111.9(9) C(24)-N(2)-C(23) 110.6(9) C(21)-N(3)-C(26) 110.8(9) C(21)-N(3)-C(25) 110.4(8) C(26)-N(3)-C(25) 107.0(9) C(26)-N(4)-C(24) 109.2(8) C(26)-N(4)-C(22) 112.1(9) C(24)-N(4)-C(22) 110.1(8) N(1)-C(2)-C(3) 129.7(9) C(4)-C(3)-C(8) 118.8(10) C(4)-C(3)-C(2) 117.3(9) C(8)-C(3)-C(2) 123.9(11) C(5)-C(4)-C(3) 122.3(10) C(4)-C(5)-C(6) 120.0(12) C(4)-C(5)-Cl(2) 120.0(9) C(6)-C(5)-Cl(2) 120.0(10) C(7)-C(6)-C(5) 120.2(11) C(6)-C(7)-C(8) 122.1(9) C(6)-C(7)-Cl(1) 120.9(8) C(8)-C(7)-Cl(1) 117.0(9) O(1)-C(8)-C(7) 119.4(8) O(1)-C(8)-C(3) 124.0(11) C(7)-C(8)-C(3) 116.6(11) C(14)-C(9)-C(10) 121.5(9) C(14)-C(9)-N(1) 119.1(8) C(10)-C(9)-N(1) 119.1(7)
205
C(11)-C(10)-C(9) 116.9(8) C(11)-C(10)-C(18) 121.1(9) C(9)-C(10)-C(18) 121.9(9) C(12)-C(11)-C(10) 121.8(9) C(11)-C(12)-C(13) 120.9(10) C(14)-C(13)-C(12) 120.2(9) C(13)-C(14)-C(9) 118.6(9) C(13)-C(14)-C(15) 122.1(8) C(9)-C(14)-C(15) 119.2(10) C(16)-C(15)-C(17) 111.7(9) C(16)-C(15)-C(14) 111.0(9)
C(17)-C(15)-C(14) 111.6(11) C(20)-C(18)-C(10) 110.0(8) C(20)-C(18)-C(19) 111.4(9) C(10)-C(18)-C(19) 111.8(10) N(3)-C(21)-P(1) 112.4(9) N(4)-C(22)-P(1) 112.3(7) N(2)-C(23)-P(1) 111.9(6) N(2)-C(24)-N(4) 113.5(9) N(2)-C(25)-N(3) 115.3(9) N(4)-C(26)-N(3) 115.2(9)
_______________________________________________________________________ Table A.19. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 3b'. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ P(1) 641(7) 6455(4) 1650(6) 63(2) N(1) 4760(15) 5516(12) 1682(15) 35(3) N(2) 1863(14) 3906(10) 1361(12) 24(2) N(3) 3417(15) 5398(9) 4232(13) 22(2) O(1) -413(14) 2576(9) 2500(11) 37(3) O(2) 5008(15) 3792(9) 5817(12) 49(3) C(1) 60(20) 4886(14) 1030(20) 45(4) C(2) 1640(20) 6324(13) 3663(15) 35(4) C(3) 3230(19) 6584(14) 1112(17) 41(4) C(4) 3931(19) 4314(14) 1008(16) 36(4) C(5) 5339(17) 5575(15) 3354(18) 33(4) C(6) 1380(20) 2813(14) 2143(18) 38(4) C(7) 3390(20) 4526(12) 5457(19) 36(4) C(8) 3200(20) 1811(14) 2320(20) 52(5) C(9) 1409(19) 4418(15) 6227(18) 44(4) _______________________________________________________________________
206
Table A.20. Bond lengths [Å] and angles [°] for 3b'. _______________________________________________________________________P(1)-C(2) 1.707(14) P(1)-C(1) 1.736(15) P(1)-C(3) 1.742(14) N(1)-C(5) 1.393(18) N(1)-C(4) 1.435(18) N(1)-C(3) 1.489(17) N(2)-C(6) 1.373(18) N(2)-C(4) 1.426(16) N(2)-C(1) 1.504(17) N(3)-C(7) 1.377(18) N(3)-C(2) 1.484(16) N(3)-C(5) 1.512(15) O(1)-C(6) 1.224(15) O(2)-C(7) 1.258(14) C(6)-C(8) 1.524(19) C(7)-C(9) 1.483(19) C(2)-P(1)-C(1) 104.0(7) C(2)-P(1)-C(3) 93.9(6) C(1)-P(1)-C(3) 98.5(7)
C(5)-N(1)-C(4) 116.9(12) C(5)-N(1)-C(3) 109.6(11) C(4)-N(1)-C(3) 111.1(9) C(6)-N(2)-C(4) 128.3(11) C(6)-N(2)-C(1) 116.0(10) C(4)-N(2)-C(1) 115.0(11) C(7)-N(3)-C(2) 124.7(11) C(7)-N(3)-C(5) 123.7(10) C(2)-N(3)-C(5) 111.4(10) N(2)-C(1)-P(1) 118.5(9) N(3)-C(2)-P(1) 119.9(10) N(1)-C(3)-P(1) 115.0(10) N(2)-C(4)-N(1) 116.9(11) N(1)-C(5)-N(3) 113.3(10) O(1)-C(6)-N(2) 124.3(12) O(1)-C(6)-C(8) 121.5(13) N(2)-C(6)-C(8) 113.6(13) O(2)-C(7)-N(3) 118.2(13) O(2)-C(7)-C(9) 122.2(15) N(3)-C(7)-C(9) 119.5(11)
_______________________________________________________________________ Table A.21. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 4d-DAPTA. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pd(1A) 9529(1) 9323(1) 7398(1) 30(1) P(1A) 10596(2) 8335(2) 8060(2) 44(1) N(1A) 11109(9) 6801(6) 8975(7) 89(4) N(2A) 11819(8) 8083(5) 9357(5) 74(3) N(3A) 12534(8) 7443(6) 7929(7) 84(3) N(4A) 8572(5) 10287(4) 6768(3) 24(1) O(1A) 13257(6) 7719(4) 10036(4) 56(2) O(2A) 13841(6) 8343(6) 7560(5) 86(3) O(3A) 10744(4) 10223(4) 7344(3) 39(1) Cl(1A) 11177(2) 13819(2) 5508(2) 57(1) Cl(2A) 12830(2) 10985(2) 7354(2) 50(1) C(1A) 11145(9) 8719(6) 8863(6) 65(3)
207
C(2A) 11797(9) 8060(7) 7521(7) 73(3) C(3A) 10206(9) 7228(6) 8580(6) 59(3) C(4A) 11396(11) 7197(7) 9617(8) 104(6) C(5A) 11999(13) 6649(8) 8450(11) 120(8) C(6A) 12743(8) 8271(6) 9611(5) 40(2) C(7A) 13539(8) 7657(8) 7945(6) 55(3) C(8A) 13163(8) 9185(6) 9317(6) 55(3) C(9A) 14278(9) 7031(7) 8417(7) 69(3) C(10A) 8421(7) 8367(6) 7500(6) 47(2) C(11A) 8903(6) 11085(5) 6488(4) 26(2) C(12A) 9933(6) 11456(5) 6523(4) 24(2) C(13A) 10068(6) 12324(5) 6095(4) 29(2) C(14A) 11006(7) 12748(5) 6059(5) 34(2) C(15A) 11859(6) 12352(5) 6448(5) 35(2) C(16A) 11747(6) 11501(5) 6878(5) 32(2) C(17A) 10779(6) 11007(5) 6933(4) 31(2) C(18A) 7483(6) 10137(5) 6594(5) 29(2) C(19A) 7307(6) 9949(5) 5877(5) 31(2) C(20A) 6254(7) 9827(5) 5720(5) 35(2) C(21A) 5419(7) 9884(5) 6272(6) 40(2) C(22A) 5622(7) 10042(6) 6985(5) 39(2) C(23A) 6645(7) 10171(5) 7168(5) 34(2) C(24A) 6860(7) 10336(6) 7969(5) 45(2) C(25A) 6486(13) 11216(8) 8060(7) 100(5) C(26A) 6302(13) 9624(9) 8621(6) 105(5) C(27A) 8234(7) 9825(6) 5290(5) 42(2) C(28A) 8358(15) 8926(8) 5245(10) 163(10) C(29A) 8113(15) 10322(13) 4505(9) 218(14) Pd(1B) 4091(1) 4397(1) 2680(1) 28(1) P(1B) 4692(2) 3531(1) 3719(1) 27(1) N(1B) 5099(6) 1982(4) 4646(4) 35(2) N(2B) 6550(5) 3048(4) 4460(4) 32(2) N(3B) 4487(5) 3139(4) 5342(4) 32(2) N(4B) 3459(5) 5309(4) 1760(4) 29(2) O(1B) 7538(5) 2791(4) 5510(3) 42(2) O(2B) 4800(5) 4288(4) 5879(3) 47(2) O(3B) 5577(4) 4999(3) 2399(3) 33(1) Cl(1B) 6529(3) 8596(2) 725(2) 78(1) Cl(2B) 7681(2) 5597(2) 2639(1) 49(1) C(1B) 6129(6) 3632(5) 3767(5) 34(2) C(2B) 4099(7) 3732(5) 4650(4) 34(2) C(3B) 4594(7) 2333(5) 3923(5) 31(2) C(4B) 6231(6) 2126(5) 4585(5) 33(2) C(5B) 4506(7) 2209(5) 5338(5) 36(2)
208
C(6B) 7196(7) 3315(6) 4957(5) 35(2) C(7B) 4839(6) 3502(6) 5926(5) 34(2) C(8B) 7455(7) 4272(6) 4813(5) 46(2) C(9B) 5251(7) 2885(6) 6616(5) 43(2) C(10B) 2688(6) 3712(6) 2960(5) 41(2) C(11B) 3957(7) 6028(5) 1417(5) 31(2) C(12B) 4995(7) 6315(5) 1551(4) 29(2) C(13B) 5265(8) 7178(5) 1153(5) 41(2) C(14B) 6224(7) 7533(6) 1233(5) 45(2) C(15B) 6960(8) 7054(6) 1691(5) 43(2) C(16B) 6730(6) 6208(5) 2077(5) 33(2) C(17B) 5741(7) 5788(5) 2029(4) 30(2) C(18B) 2408(6) 5211(5) 1507(5) 33(2) C(19B) 2280(7) 4708(5) 971(5) 35(2) C(20B) 1265(7) 4625(6) 738(5) 40(2) C(21B) 400(7) 5047(6) 1046(5) 45(2) C(22B) 541(7) 5506(7) 1590(6) 57(3) C(23B) 1543(8) 5627(7) 1829(6) 56(3) C(24B) 1740(10) 6098(11) 2546(12) 116(7) C(25B) 1410(20) 7042(11) 2211(9) 218(15) C(26B) 1020(20) 5811(12) 3232(9) 174(11) C(27B) 3229(7) 4266(6) 622(5) 38(2) C(28B) 3021(9) 3325(7) 573(6) 60(3) C(29B) 3618(8) 4825(7) -176(6) 57(3) C(1S) 602(11) 1184(10) 9003(6) 43(3) C(2S) 10006(11) 2948(10) 4019(7) 93(5) Cl(2') 637(7) 2083(7) 9362(5) 134(5) Cl(1S) -786(5) 747(5) 9062(4) 181(3) Cl(2S) 492(19) 1340(20) 8933(17) 296(17) Cl(3S) 9328(5) 2050(5) 4234(3) 179(3) Cl(4S) 9449(5) 3890(5) 3205(3) 192(3) O(1W) -1199(5) -51(5) 9447(4) 55(2) _______________________________________________________________________ Table A.22. Bond lengths [Å] and angles [°] for 4d-DAPTA. _______________________________________________________________________ Pd(1A)-C(10A) 2.031(8) Pd(1A)-O(3A) 2.077(5) Pd(1A)-N(4A) 2.080(6) Pd(1A)-P(1A) 2.209(2) P(1A)-C(2A) 1.816(12) P(1A)-C(1A) 1.827(10) P(1A)-C(3A) 1.831(8)
N(1A)-C(5A) 1.45(2) N(1A)-C(3A) 1.445(13) N(1A)-C(4A) 1.467(17) N(2A)-C(6A) 1.330(12) N(2A)-C(4A) 1.459(12) N(2A)-C(1A) 1.467(12) N(3A)-C(7A) 1.313(14)
209
N(3A)-C(2A) 1.434(13) N(3A)-C(5A) 1.511(17) N(4A)-C(11A) 1.303(9) N(4A)-C(18A) 1.453(10) O(1A)-C(6A) 1.218(11) O(2A)-C(7A) 1.190(13) O(3A)-C(17A) 1.280(9) Cl(1A)-C(14A) 1.751(8) Cl(2A)-C(16A) 1.737(8) C(6A)-C(8A) 1.502(12) C(7A)-C(9A) 1.491(14) C(11A)-C(12A) 1.436(10) C(12A)-C(13A) 1.409(10) C(12A)-C(17A) 1.413(11) C(13A)-C(14A) 1.351(11) C(14A)-C(15A) 1.373(12) C(15A)-C(16A) 1.385(11) C(16A)-C(17A) 1.436(11) C(18A)-C(19A) 1.388(11) C(18A)-C(23A) 1.412(11) C(19A)-C(20A) 1.392(11) C(19A)-C(27A) 1.535(11) C(20A)-C(21A) 1.390(12) C(21A)-C(22A) 1.370(12) C(22A)-C(23A) 1.372(11) C(23A)-C(24A) 1.528(12) C(24A)-C(25A) 1.481(14) C(24A)-C(26A) 1.552(14) C(27A)-C(28A) 1.428(15) C(27A)-C(29A) 1.447(15) Pd(1B)-C(10B) 2.050(8) Pd(1B)-O(3B) 2.083(5) Pd(1B)-N(4B) 2.101(6) Pd(1B)-P(1B) 2.195(2) P(1B)-C(1B) 1.820(8) P(1B)-C(3B) 1.832(8) P(1B)-C(2B) 1.836(8) N(1B)-C(4B) 1.434(10) N(1B)-C(3B) 1.454(10) N(1B)-C(5B) 1.485(10) N(2B)-C(6B) 1.367(10) N(2B)-C(4B) 1.468(10) N(2B)-C(1B) 1.477(10) N(3B)-C(7B) 1.378(10)
N(3B)-C(5B) 1.454(10) N(3B)-C(2B) 1.466(10) N(4B)-C(11B) 1.303(10) N(4B)-C(18B) 1.440(10) O(1B)-C(6B) 1.225(10) O(2B)-C(7B) 1.213(10) O(3B)-C(17B) 1.277(9) Cl(1B)-C(14B) 1.744(9) Cl(2B)-C(16B) 1.737(8) C(6B)-C(8B) 1.499(12) C(7B)-C(9B) 1.493(12) C(11B)-C(12B) 1.436(11) C(12B)-C(13B) 1.413(11) C(12B)-C(17B) 1.428(11) C(13B)-C(14B) 1.361(12) C(14B)-C(15B) 1.370(13) C(15B)-C(16B) 1.375(11) C(16B)-C(17B) 1.430(11) C(18B)-C(19B) 1.370(11) C(18B)-C(23B) 1.401(12) C(19B)-C(20B) 1.381(12) C(19B)-C(27B) 1.521(12) C(20B)-C(21B) 1.394(13) C(21B)-C(22B) 1.336(13) C(22B)-C(23B) 1.381(13) C(23B)-C(24B) 1.626(18) C(24B)-C(26B) 1.45(2) C(24B)-C(25B) 1.53(2) C(27B)-C(28B) 1.519(12) C(27B)-C(29B) 1.536(12) C(1S)-Cl(2') 1.662(17) C(1S)-Cl(1S) 1.869(15) C(2S)-Cl(3S) 1.614(13) C(2S)-Cl(4S) 1.972(15) Cl(2')-Cl(2S) 1.54(3) Cl(1S)-Cl(2S) 1.84(2) C(10A)-Pd(1A)-O(3A) 175.3(3) C(10A)-Pd(1A)-N(4A) 93.7(3) O(3A)-Pd(1A)-N(4A) 90.9(2) C(10A)-Pd(1A)-P(1A) 88.4(3) O(3A)-Pd(1A)-P(1A) 86.94(16) N(4A)-Pd(1A)-P(1A) 177.86(17) C(2A)-P(1A)-C(1A) 102.1(6)
210
C(2A)-P(1A)-C(3A) 98.7(5) C(1A)-P(1A)-C(3A) 99.1(5) C(2A)-P(1A)-Pd(1A) 116.0(4) C(1A)-P(1A)-Pd(1A) 111.8(4) C(3A)-P(1A)-Pd(1A) 125.6(3) C(5A)-N(1A)-C(3A) 113.6(11) C(5A)-N(1A)-C(4A) 114.8(11) C(3A)-N(1A)-C(4A) 113.0(12) C(6A)-N(2A)-C(4A) 118.8(8) C(6A)-N(2A)-C(1A) 124.8(8) C(4A)-N(2A)-C(1A) 116.3(8) C(7A)-N(3A)-C(2A) 120.4(10) C(7A)-N(3A)-C(5A) 124.8(10) C(2A)-N(3A)-C(5A) 113.6(10) C(11A)-N(4A)-C(18A) 113.7(6) C(11A)-N(4A)-Pd(1A) 122.5(5) C(18A)-N(4A)-Pd(1A) 123.7(5) C(17A)-O(3A)-Pd(1A) 126.3(5) N(2A)-C(1A)-P(1A) 115.3(8) N(3A)-C(2A)-P(1A) 118.2(9) N(1A)-C(3A)-P(1A) 109.0(6) N(2A)-C(4A)-N(1A) 113.6(9) N(1A)-C(5A)-N(3A) 117.4(11) O(1A)-C(6A)-N(2A) 121.9(8) O(1A)-C(6A)-C(8A) 120.9(9) N(2A)-C(6A)-C(8A) 117.2(8) O(2A)-C(7A)-N(3A) 118.5(11) O(2A)-C(7A)-C(9A) 121.7(11) N(3A)-C(7A)-C(9A) 119.8(11) N(4A)-C(11A)-C(12A) 129.0(7) C(13A)-C(12A)-C(17A) 120.4(7) C(13A)-C(12A)-C(11A) 114.9(7) C(17A)-C(12A)-C(11A) 124.6(7) C(14A)-C(13A)-C(12A) 121.4(7) C(13A)-C(14A)-C(15A) 121.2(7) C(13A)-C(14A)-Cl(1A) 121.0(7) C(15A)-C(14A)-Cl(1A) 117.8(7) C(14A)-C(15A)-C(16A) 118.8(8) C(15A)-C(16A)-C(17A) 123.0(7) C(15A)-C(16A)-Cl(2A) 119.2(6) C(17A)-C(16A)-Cl(2A) 117.8(6) O(3A)-C(17A)-C(12A) 125.8(7) O(3A)-C(17A)-C(16A) 119.0(7) C(12A)-C(17A)-C(16A) 115.2(7)
C(19A)-C(18A)-C(23A) 122.4(7) C(19A)-C(18A)-N(4A) 118.9(7) C(23A)-C(18A)-N(4A) 118.7(7) C(18A)-C(19A)-C(20A) 117.6(8) C(18A)-C(19A)-C(27A) 121.8(7) C(20A)-C(19A)-C(27A) 120.5(7) C(19A)-C(20A)-C(21A) 120.5(8) C(22A)-C(21A)-C(20A) 120.5(8) C(21A)-C(22A)-C(23A) 121.3(8) C(22A)-C(23A)-C(18A) 117.6(8) C(22A)-C(23A)-C(24A) 120.7(8) C(18A)-C(23A)-C(24A) 121.6(7) C(25A)-C(24A)-C(23A) 111.8(8) C(25A)-C(24A)-C(26A) 109.6(10) C(23A)-C(24A)-C(26A) 109.9(9) C(28A)-C(27A)-C(29A) 107.0(13) C(28A)-C(27A)-C(19A) 111.4(8) C(29A)-C(27A)-C(19A) 113.8(9) C(10B)-Pd(1B)-O(3B) 175.5(3) C(10B)-Pd(1B)-N(4B) 93.5(3) O(3B)-Pd(1B)-N(4B) 89.5(2) C(10B)-Pd(1B)-P(1B) 86.4(2) O(3B)-Pd(1B)-P(1B) 91.01(15) N(4B)-Pd(1B)-P(1B) 174.26(18) C(1B)-P(1B)-C(3B) 99.2(4) C(1B)-P(1B)-C(2B) 105.2(4) C(3B)-P(1B)-C(2B) 99.5(4) C(1B)-P(1B)-Pd(1B) 112.4(3) C(3B)-P(1B)-Pd(1B) 123.6(3) C(2B)-P(1B)-Pd(1B) 114.4(3) C(4B)-N(1B)-C(3B) 113.3(6) C(4B)-N(1B)-C(5B) 115.6(7) C(3B)-N(1B)-C(5B) 112.7(7) C(6B)-N(2B)-C(4B) 120.6(6) C(6B)-N(2B)-C(1B) 124.4(7) C(4B)-N(2B)-C(1B) 115.0(6) C(7B)-N(3B)-C(5B) 125.1(7) C(7B)-N(3B)-C(2B) 118.1(7) C(5B)-N(3B)-C(2B) 116.7(6) C(11B)-N(4B)-C(18B) 115.5(7) C(11B)-N(4B)-Pd(1B) 122.4(5) C(18B)-N(4B)-Pd(1B) 121.9(5) C(17B)-O(3B)-Pd(1B) 125.9(5) N(2B)-C(1B)-P(1B) 113.2(5)
211
N(3B)-C(2B)-P(1B) 114.1(5) N(1B)-C(3B)-P(1B) 108.1(5) N(1B)-C(4B)-N(2B) 115.0(7) N(3B)-C(5B)-N(1B) 114.5(6) O(1B)-C(6B)-N(2B) 120.9(8) O(1B)-C(6B)-C(8B) 121.2(8) N(2B)-C(6B)-C(8B) 117.8(7) O(2B)-C(7B)-N(3B) 120.8(8) O(2B)-C(7B)-C(9B) 122.2(8) N(3B)-C(7B)-C(9B) 117.0(8) N(4B)-C(11B)-C(12B) 128.4(8) C(13B)-C(12B)-C(17B) 120.3(8) C(13B)-C(12B)-C(11B) 115.1(7) C(17B)-C(12B)-C(11B) 124.6(7) C(14B)-C(13B)-C(12B) 121.1(8) C(13B)-C(14B)-C(15B) 120.6(8) C(13B)-C(14B)-Cl(1B) 119.6(7) C(15B)-C(14B)-Cl(1B) 119.8(7) C(14B)-C(15B)-C(16B) 119.9(8) C(15B)-C(16B)-C(17B) 123.1(8) C(15B)-C(16B)-Cl(2B) 119.5(7) C(17B)-C(16B)-Cl(2B) 117.4(6) O(3B)-C(17B)-C(16B) 120.1(7) O(3B)-C(17B)-C(12B) 124.8(7)
C(16B)-C(17B)-C(12B) 115.1(7) C(19B)-C(18B)-C(23B) 122.0(8) C(19B)-C(18B)-N(4B) 119.5(7) C(23B)-C(18B)-N(4B) 118.5(8) C(18B)-C(19B)-C(20B) 118.3(8) C(18B)-C(19B)-C(27B) 121.4(8) C(20B)-C(19B)-C(27B) 120.3(8) C(19B)-C(20B)-C(21B) 120.2(8) C(22B)-C(21B)-C(20B) 120.3(9) C(21B)-C(22B)-C(23B) 121.8(10) C(22B)-C(23B)-C(18B) 117.3(9) C(22B)-C(23B)-C(24B) 123.4(9) C(18B)-C(23B)-C(24B) 118.7(8) C(26B)-C(24B)-C(25B) 105.2(12) C(26B)-C(24B)-C(23B) 114.1(13) C(25B)-C(24B)-C(23B) 101.6(15) C(19B)-C(27B)-C(28B) 113.9(8) C(19B)-C(27B)-C(29B) 110.1(7) C(28B)-C(27B)-C(29B) 111.6(7) Cl(2')-C(1S)-Cl(1S) 111.9(8) Cl(3S)-C(2S)-Cl(4S) 116.0(7) Cl(2S)-Cl(2')-C(1S) 9.1(15) Cl(2S)-Cl(1S)-C(1S) 8.7(14) Cl(2')-Cl(2S)-Cl(1S) 119.8(17)
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212
APPENDIX B
BOND DISTANCES AND ANGLES CORRESPONDING TO SOLID STATE
STRUCTURES IN CHAPTER III*
Table B.1. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ P(1) 641(7) 6455(4) 1650(6) 63(2) N(1) 4760(15) 5516(12) 1682(15) 35(3) N(2) 1863(14) 3906(10) 1361(12) 24(2) N(3) 3417(15) 5398(9) 4232(13) 22(2) O(1) -413(14) 2576(9) 2500(11) 37(3) O(2) 5008(15) 3792(9) 5817(12) 49(3) C(1) 60(20) 4886(14) 1030(20) 45(4) C(2) 1640(20) 6324(13) 3663(15) 35(4) C(3) 3230(19) 6584(14) 1112(17) 41(4) C(4) 3931(19) 4314(14) 1008(16) 36(4) C(5) 5339(17) 5575(15) 3354(18) 33(4) C(6) 1380(20) 2813(14) 2143(18) 38(4) C(7) 3390(20) 4526(12) 5457(19) 36(4) C(8) 3200(20) 1811(14) 2320(20) 52(5) C(9) 1409(19) 4418(15) 6227(18) 44(4) _______________________________________________________________________ _______________ * Appear in the order in which they are described in the chapter.
213
Table B.2. Bond lengths [Å] and angles [°] for 1. _______________________________________________________________________ P(1)-C(2) 1.707(14) P(1)-C(1) 1.736(15) P(1)-C(3) 1.742(14) N(1)-C(5) 1.393(18) N(1)-C(4) 1.435(18) N(1)-C(3) 1.489(17) N(2)-C(6) 1.373(18) N(2)-C(4) 1.426(16) N(2)-C(1) 1.504(17) N(3)-C(7) 1.377(18) N(3)-C(2) 1.484(16) N(3)-C(5) 1.512(15) O(1)-C(6) 1.224(15) O(2)-C(7) 1.258(14) C(6)-C(8) 1.524(19) C(7)-C(9) 1.483(19) C(2)-P(1)-C(1) 104.0(7) C(2)-P(1)-C(3) 93.9(6) C(1)-P(1)-C(3) 98.5(7)
C(5)-N(1)-C(4) 116.9(12) C(5)-N(1)-C(3) 109.6(11) C(4)-N(1)-C(3) 111.1(9) C(6)-N(2)-C(4) 128.3(11) C(6)-N(2)-C(1) 116.0(10) C(4)-N(2)-C(1) 115.0(11) C(7)-N(3)-C(2) 124.7(11) C(7)-N(3)-C(5) 123.7(10) C(2)-N(3)-C(5) 111.4(10) N(2)-C(1)-P(1) 118.5(9) N(3)-C(2)-P(1) 119.9(10) N(1)-C(3)-P(1) 115.0(10) N(2)-C(4)-N(1) 116.9(11) N(1)-C(5)-N(3) 113.3(10) O(1)-C(6)-N(2) 124.3(12) O(1)-C(6)-C(8) 121.5(13) N(2)-C(6)-C(8) 113.6(13) O(2)-C(7)-N(3) 118.2(13) O(2)-C(7)-C(9) 122.2(15) N(3)-C(7)-C(9) 119.5(11)
_______________________________________________________________________ Table B.3. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 5. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ W(1) 668(1) 2399(1) 1812(1) 27(1) P(1) 2700(3) 1515(2) 2379(2) 26(1) N(1) 4880(8) 805(6) 4005(7) 27(2) N(2) 5108(8) 1922(7) 2582(7) 29(2) N(3) 4001(8) -189(6) 2216(7) 30(2) O(1) 5264(7) 2267(6) 996(6) 31(2) O(2) 5653(7) -508(6) 1883(6) 37(2) O(3) -1804(7) 3692(6) 1218(7) 44(2) O(4) 1544(9) 4245(7) 712(8) 56(2) O(5) -514(9) 1317(8) -589(9) 72(3) O(6) 1872(8) 3421(7) 4238(8) 53(2) O(7) -268(9) 522(7) 2800(9) 68(3)
214
C(1) 3819(10) 2273(8) 2081(9) 27(3) C(2) 2735(10) 197(8) 1849(9) 29(3) C(3) 3689(10) 1214(9) 3873(9) 33(3) C(4) 5647(9) 1554(7) 3799(8) 24(2) C(5) 4737(11) -190(8) 3446(9) 32(3) C(6) 5761(10) 1993(8) 1980(9) 28(3) C(7) 4526(11) -390(8) 1522(9) 29(3) C(8) 7142(10) 1706(9) 2567(10) 39(3) C(9) 3689(11) -488(9) 271(9) 39(3) C(10) -939(12) 3209(9) 1417(10) 37(3) C(11) 1240(10) 3580(9) 1113(10) 36(3) C(12) -79(11) 1711(10) 306(11) 43(3) C(13) 1436(11) 3080(10) 3352(11) 36(3) C(14) 75(10) 1187(10) 2436(11) 40(3) _______________________________________________________________________ Table B.4. Bond lengths [Å] and angles [°] for 5. _______________________________________________________________________ W(1)-C(12) 1.999(13) W(1)-C(13) 2.032(13) W(1)-C(14) 2.040(13) W(1)-C(10) 2.049(14) W(1)-C(11) 2.053(13) W(1)-P(1) 2.492(3) P(1)-C(1) 1.840(11) P(1)-C(3) 1.845(11) P(1)-C(2) 1.849(10) N(1)-C(4) 1.442(12) N(1)-C(5) 1.455(13) N(1)-C(3) 1.460(13) N(2)-C(6) 1.344(13) N(2)-C(1) 1.462(13) N(2)-C(4) 1.524(13) N(3)-C(7) 1.348(13) N(3)-C(2) 1.464(13) N(3)-C(5) 1.472(14) O(1)-C(6) 1.224(13) O(2)-C(7) 1.230(12) O(3)-C(10) 1.138(13) O(4)-C(11) 1.150(13) O(5)-C(12) 1.180(14) O(6)-C(13) 1.142(14) O(7)-C(14) 1.146(14)
C(6)-C(8) 1.535(15) C(7)-C(9) 1.519(15) C(12)-W(1)-C(13) 179.2(5) C(12)-W(1)-C(14) 88.8(5) C(13)-W(1)-C(14) 90.6(5) C(12)-W(1)-C(10) 90.8(5) C(13)-W(1)-C(10) 89.8(5) C(14)-W(1)-C(10) 92.2(4) C(12)-W(1)-C(11) 88.5(5) C(13)-W(1)-C(11) 92.1(5) C(14)-W(1)-C(11) 177.3(5) C(10)-W(1)-C(11) 88.3(4) C(12)-W(1)-P(1) 92.7(4) C(13)-W(1)-P(1) 86.8(3) C(14)-W(1)-P(1) 89.7(3) C(10)-W(1)-P(1) 176.1(3) C(11)-W(1)-P(1) 90.0(3) C(1)-P(1)-C(3) 99.0(5) C(1)-P(1)-C(2) 105.6(5) C(3)-P(1)-C(2) 95.8(5) C(1)-P(1)-W(1) 113.6(3) C(3)-P(1)-W(1) 120.2(4) C(2)-P(1)-W(1) 119.3(4) C(4)-N(1)-C(5) 116.1(8)
215
C(4)-N(1)-C(3) 114.0(8) C(5)-N(1)-C(3) 111.6(9) C(6)-N(2)-C(1) 119.1(9) C(6)-N(2)-C(4) 124.1(9) C(1)-N(2)-C(4) 116.7(8) C(7)-N(3)-C(2) 124.5(9) C(7)-N(3)-C(5) 121.4(9) C(2)-N(3)-C(5) 113.4(8) N(2)-C(1)-P(1) 117.6(7) N(3)-C(2)-P(1) 112.4(7) N(1)-C(3)-P(1) 109.8(7) N(1)-C(4)-N(2) 113.6(8)
N(1)-C(5)-N(3) 116.2(9) O(1)-C(6)-N(2) 120.9(10) O(1)-C(6)-C(8) 121.4(10) N(2)-C(6)-C(8) 117.7(9) O(2)-C(7)-N(3) 121.5(10) O(2)-C(7)-C(9) 120.0(10) N(3)-C(7)-C(9) 118.5(10) O(3)-C(10)-W(1) 177.2(10) O(4)-C(11)-W(1) 179.0(11) O(5)-C(12)-W(1) 179.1(12) O(6)-C(13)-W(1) 177.1(11) O(7)-C(14)-W(1) 178.4(11)
_______________________________________________________________________ Table B.5. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 6. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Cr(1) 11260(1) 7861(1) 3347(1) 23(1) P(1) 9714(1) 8875(1) 3583(1) 21(1) N(1) 7598(2) 9455(2) 3296(1) 26(1) N(2) 8958(2) 10792(2) 3469(1) 27(1) N(3) 8018(2) 9472(2) 4372(1) 24(1) O(1) 7906(2) 11937(2) 3928(1) 38(1) O(2) 8554(2) 10014(2) 5280(1) 35(1) O(3) 13285(2) 6743(2) 2908(1) 37(1) O(4) 12839(2) 9616(2) 3398(1) 42(1) O(5) 11812(3) 7330(2) 4632(1) 65(1) O(6) 10521(2) 8196(2) 2066(1) 43(1) O(7) 9847(2) 6005(2) 3323(1) 61(1) C(1) 9968(3) 10183(2) 3420(1) 26(1) C(2) 9049(2) 8877(2) 4325(1) 24(1) C(3) 8424(2) 8707(2) 3140(1) 26(1) C(4) 7970(3) 10430(2) 3136(1) 31(1) C(5) 7160(2) 9347(2) 3895(1) 27(1) C(6) 8836(3) 11549(2) 3856(1) 28(1) C(7) 7836(3) 9974(2) 4886(1) 27(1) C(8) 9867(3) 11908(2) 4181(1) 34(1) C(9) 6708(3) 10477(3) 4964(2) 41(1) C(10) 12506(3) 7149(2) 3086(1) 26(1)
216
C(11) 12230(3) 8975(2) 3380(1) 28(1) C(12) 11601(3) 7559(2) 4156(2) 36(1) C(13) 10824(3) 8093(2) 2543(2) 29(1) C(14) 10345(3) 6719(2) 3335(2) 36(1) _______________________________________________________________________ Table B.6. Bond lengths [Å] and angles [°] for 6. _______________________________________________________________________ Cr(1)-C(10) 1.863(4) Cr(1)-C(12) 1.902(4) Cr(1)-C(13) 1.902(4) Cr(1)-C(14) 1.903(4) Cr(1)-C(11) 1.910(4) Cr(1)-P(1) 2.3562(19) P(1)-C(2) 1.839(3) P(1)-C(3) 1.836(3) P(1)-C(1) 1.853(3) N(1)-C(4) 1.451(4) N(1)-C(3) 1.458(4) N(1)-C(5) 1.447(4) N(2)-C(6) 1.359(4) N(2)-C(1) 1.462(4) N(2)-C(4) 1.473(4) N(3)-C(7) 1.359(4) N(3)-C(2) 1.471(4) N(3)-C(5) 1.484(4) O(1)-C(6) 1.233(4) O(2)-C(7) 1.227(4) O(3)-C(10) 1.148(4) O(4)-C(11) 1.136(4) O(5)-C(12) 1.140(4) O(6)-C(13) 1.136(4) O(7)-C(14) 1.141(4) C(6)-C(8) 1.504(5) C(7)-C(9) 1.512(5) C(10)-Cr(1)-C(12) 91.00(14) C(10)-Cr(1)-C(13) 90.22(14) C(12)-Cr(1)-C(13) 175.55(14) C(10)-Cr(1)-C(14) 90.89(15) C(12)-Cr(1)-C(14) 87.43(15) C(13)-Cr(1)-C(14) 88.26(14) C(10)-Cr(1)-C(11) 87.37(15)
C(12)-Cr(1)-C(11) 90.53(14) C(13)-Cr(1)-C(11) 93.81(13) C(14)-Cr(1)-C(11) 177.30(14) C(10)-Cr(1)-P(1) 173.55(10) C(12)-Cr(1)-P(1) 94.56(11) C(13)-Cr(1)-P(1) 84.48(10) C(14)-Cr(1)-P(1) 92.62(13) C(11)-Cr(1)-P(1) 89.31(12) C(2)-P(1)-C(3) 97.62(15) C(2)-P(1)-C(1) 104.26(14) C(3)-P(1)-C(1) 98.58(14) C(2)-P(1)-Cr(1) 122.43(10) C(3)-P(1)-Cr(1) 116.78(11) C(1)-P(1)-Cr(1) 113.53(11) C(4)-N(1)-C(3) 112.6(2) C(4)-N(1)-C(5) 115.5(2) C(3)-N(1)-C(5) 113.0(2) C(6)-N(2)-C(1) 124.7(3) C(6)-N(2)-C(4) 119.7(3) C(1)-N(2)-C(4) 114.8(2) C(7)-N(3)-C(2) 118.2(2) C(7)-N(3)-C(5) 124.1(2) C(2)-N(3)-C(5) 116.9(2) N(2)-C(1)-P(1) 113.8(2) N(3)-C(2)-P(1) 114.93(19) N(1)-C(3)-P(1) 109.9(2) N(1)-C(4)-N(2) 115.2(2) N(1)-C(5)-N(3) 114.3(2) O(1)-C(6)-N(2) 120.6(3) O(1)-C(6)-C(8) 121.3(3) N(2)-C(6)-C(8) 118.2(3) O(2)-C(7)-N(3) 121.5(3) O(2)-C(7)-C(9) 120.5(3) N(3)-C(7)-C(9) 117.9(3) O(3)-C(10)-Cr(1) 177.0(3)
217
O(4)-C(11)-Cr(1) 177.6(3) O(5)-C(12)-Cr(1) 176.6(3)
O(6)-C(13)-Cr(1) 176.4(3) O(7)-C(14)-Cr(1) 176.4(3)
_______________________________________________________________________ Table B.7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 2. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ P(1) 10249(1) 1860(1) 4656(1) 21(1) N(1) 11830(2) 1485(2) 3711(1) 24(1) N(2) 11196(3) 3603(2) 3914(1) 23(1) N(3) 8975(3) 1677(2) 3573(1) 25(1) O(1) 9213(3) 4934(2) 3871(1) 45(1) O(2) 8275(2) 2156(2) 2674(1) 35(1) O(3) 9878(2) 1621(2) 5265(1) 28(1) C(1) 10870(3) 3397(2) 4520(1) 26(1) C(2) 8604(3) 1554(3) 4177(1) 29(1) C(3) 11789(3) 1038(2) 4305(1) 26(1) C(4) 12311(3) 2737(2) 3665(1) 25(1) C(5) 10467(3) 1141(2) 3379(1) 26(1) C(6) 10264(3) 4390(2) 3622(1) 29(1) C(7) 7953(3) 2141(2) 3186(1) 25(1) C(8) 10561(4) 4584(3) 3000(1) 36(1) C(9) 6441(3) 2665(3) 3400(1) 33(1) _______________________________________________________________________ Table B.8. Bond lengths [Å] and angles [°] for 2. _______________________________________________________________________ P(1)-O(3) 1.492(3) P(1)-C(3) 1.797(3) P(1)-C(1) 1.816(3) P(1)-C(2) 1.827(3) N(1)-C(5) 1.448(4) N(1)-C(4) 1.456(4) N(1)-C(3) 1.483(4) N(2)-C(6) 1.365(4) N(2)-C(1) 1.471(4) N(2)-C(4) 1.474(4) N(3)-C(7) 1.360(4) N(3)-C(2) 1.461(4)
N(3)-C(5) 1.475(4) O(1)-C(6) 1.227(4) O(2)-C(7) 1.236(4) C(6)-C(8) 1.500(5) C(7)-C(9) 1.499(4) O(3)-P(1)-C(3) 120.30(13) O(3)-P(1)-C(1) 113.43(13) C(3)-P(1)-C(1) 100.76(15) O(3)-P(1)-C(2) 113.33(14) C(3)-P(1)-C(2) 100.42(16) C(1)-P(1)-C(2) 106.84(14)
218
C(5)-N(1)-C(4) 115.9(2) C(5)-N(1)-C(3) 113.6(2) C(4)-N(1)-C(3) 113.4(2) C(6)-N(2)-C(1) 118.5(2) C(6)-N(2)-C(4) 126.4(2) C(1)-N(2)-C(4) 113.9(2) C(7)-N(3)-C(2) 123.3(2) C(7)-N(3)-C(5) 119.7(2) C(2)-N(3)-C(5) 116.6(2) N(2)-C(1)-P(1) 111.80(18)
N(3)-C(2)-P(1) 114.57(19) N(1)-C(3)-P(1) 106.19(18) N(1)-C(4)-N(2) 114.5(2) N(1)-C(5)-N(3) 114.5(2) O(1)-C(6)-N(2) 120.0(3) O(1)-C(6)-C(8) 121.1(3) N(2)-C(6)-C(8) 119.0(3) O(2)-C(7)-N(3) 121.1(3) O(2)-C(7)-C(9) 120.8(3) N(3)-C(7)-C(9) 118.1(3)
_______________________________________________________________________
219
APPENDIX C
BOND DISTANCES AND ANGLES CORRESPONDING TO SOLID STATE
STRUCTURES IN CHAPTER IV*
Table C.1. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 2.THF. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Cr(1) 2131(1) 5447(1) 892(1) 20(1) N(1) 1196(3) 5251(2) -324(4) 21(1) N(2) 1790(3) 6159(2) 364(4) 23(1) O(1) 2416(3) 4740(2) 1185(4) 25(1) O(2) 3034(3) 5701(2) 1930(4) 23(1) O(3) 2916(3) 5449(2) -397(4) 25(1) Br(1) 1205(1) 5512(1) 2334(1) 42(1) C(1) 768(4) 5686(2) -869(6) 24(2) C(2) 979(4) 4788(2) -574(6) 24(2) C(3) 1368(4) 4328(2) -126(6) 23(2) C(4) 2072(4) 4320(2) 733(6) 25(2) C(5) 2407(4) 3832(2) 1100(6) 24(2) C(6) 2055(4) 3411(2) 588(6) 23(2) C(7) 1362(4) 3404(3) -290(6) 28(2) C(8) 1039(4) 3860(2) -597(6) 26(2) C(9) 1057(5) 2899(3) -864(6) 30(2) C(10) 251(5) 2974(3) -1667(7) 37(2) C(11) 900(5) 2496(2) 39(7) 35(2) C(12) 1714(5) 2692(3) -1536(7) 47(2) C(13) 3135(4) 3808(2) 2093(6) 30(2) C(14) 2875(5) 4038(3) 3187(6) 37(2) C(15) 3882(4) 4084(3) 1756(7) 37(2) C(16) 3401(5) 3248(3) 2373(7) 41(2) C(17) 1088(4) 6165(2) -521(5) 21(2) _______________ * Appear in the order in which they are described in the chapter.
220
C(18) 2131(4) 6567(2) 823(5) 20(2) C(19) 2800(4) 6603(2) 1732(6) 22(2) C(20) 3216(4) 6168(2) 2298(6) 24(2) C(21) 3824(4) 6257(2) 3261(5) 21(2) C(22) 4035(4) 6755(2) 3563(6) 26(2) C(23) 3680(4) 7189(2) 2993(6) 25(2) C(24) 3057(4) 7098(2) 2086(6) 24(2) C(25) 3928(4) 7737(2) 3347(6) 28(2) C(26) 4161(5) 8028(3) 2310(6) 35(2) C(27) 3206(5) 8001(3) 3783(7) 47(2) C(28) 4662(6) 7748(3) 4299(7) 48(2) C(29) 4244(4) 5800(3) 3964(6) 29(2) C(30) 4849(5) 5973(3) 4989(6) 38(2) C(31) 3588(5) 5479(3) 4437(6) 36(2) C(32) 4721(5) 5476(3) 3179(6) 31(2) C(33) 726(4) 6604(2) -1010(6) 25(2) C(34) 42(4) 6565(3) -1829(6) 28(2) C(35) -277(4) 6097(3) -2182(6) 28(2) C(36) 95(4) 5657(3) -1703(6) 27(2) C(37) 2692(6) 5361(5) -1589(8) 77(3) C(38) 3470(5) 5392(3) -2111(7) 46(2) C(39) 4118(5) 5285(4) -1140(7) 63(3) C(40) 3792(5) 5407(4) -139(8) 64(3) C(1S) 4048(10) 3159(5) 7794(15) 113(5) C(2S) 3782(15) 3202(6) 6748(13) 145(8) C(3S) 3064(11) 3475(11) 6556(18) 170(10) C(4S) 3133(9) 3838(6) 7550(20) 145(8) C(5S) 884(8) 4284(6) 6400(11) 103(4) C(6S) 1006(11) 4145(5) 5213(11) 123(6) C(7S) 1490(16) 4603(5) 4921(14) 186(12) C(8S) 1420(12) 4970(5) 5659(12) 135(7) C(9S) 1626(6) 6420(3) 6007(8) 51(2) C(10S) 1800(13) 6399(5) 4833(10) 154(8) C(11S) 1642(6) 6874(3) 4273(7) 59(3) C(12S) 1494(4) 7225(2) 5123(5) 14(1) O(1S) 3796(10) 3600(6) 8517(11) 193(6) O(2S) 1300(12) 4719(6) 6681(9) 205(7) O(3S) 1241(5) 6952(3) 6040(9) 109(3) _______________________________________________________________________
221
Table C.2. Bond lengths [Å] and angles [°] for 2.THF. _______________________________________________________________________ Cr(1)-O(2) 1.898(4) Cr(1)-O(1) 1.927(4) Cr(1)-N(1) 2.006(5) Cr(1)-N(2) 2.019(5) Cr(1)-O(3) 2.117(5) Cr(1)-Br(1) 2.4320(16) N(1)-C(2) 1.284(8) N(1)-C(1) 1.439(8) N(2)-C(18) 1.286(8) N(2)-C(17) 1.436(8) O(1)-C(4) 1.314(8) O(2)-C(20) 1.317(7) O(3)-C(37) 1.413(10) O(3)-C(40) 1.429(10) C(1)-C(36) 1.368(9) C(1)-C(17) 1.398(9) C(2)-C(3) 1.427(9) C(3)-C(8) 1.418(9) C(3)-C(4) 1.421(9) C(4)-C(5) 1.431(9) C(5)-C(6) 1.345(9) C(5)-C(13) 1.546(9) C(6)-C(7) 1.422(9) C(7)-C(8) 1.335(9) C(7)-C(9) 1.534(9) C(9)-C(11) 1.542(10) C(9)-C(12) 1.521(10) C(9)-C(10) 1.522(10) C(13)-C(15) 1.522(10) C(13)-C(14) 1.531(10) C(13)-C(16) 1.551(9) C(17)-C(33) 1.381(9) C(18)-C(19) 1.420(9) C(19)-C(20) 1.440(9) C(19)-C(24) 1.407(9) C(20)-C(21) 1.416(9) C(21)-C(22) 1.382(9) C(21)-C(29) 1.556(9) C(22)-C(23) 1.401(9) C(23)-C(24) 1.386(9) C(23)-C(25) 1.532(9) C(25)-C(28) 1.521(10)
C(25)-C(27) 1.520(11) C(25)-C(26) 1.528(10) C(29)-C(31) 1.528(10) C(29)-C(30) 1.515(9) C(29)-C(32) 1.543(10) C(33)-C(34) 1.372(9) C(34)-C(35) 1.373(9) C(35)-C(36) 1.385(9) C(37)-C(38) 1.492(12) C(38)-C(39) 1.470(12) C(39)-C(40) 1.393(12) C(1S)-C(2S) 1.247(16) C(1S)-O(1S) 1.523(17) C(2S)-C(3S) 1.37(2) C(3S)-C(4S) 1.50(2) C(4S)-O(1S) 1.58(2) C(5S)-O(2S) 1.343(16) C(5S)-C(6S) 1.479(17) C(6S)-C(7S) 1.503(19) C(7S)-C(8S) 1.308(17) C(8S)-O(2S) 1.405(15) C(9S)-C(10S) 1.445(15) C(9S)-O(3S) 1.530(10) C(10S)-C(11S) 1.414(14) C(11S)-C(12S) 1.401(10) C(12S)-O(3S) 1.401(11) O(2)-Cr(1)-O(1) 94.25(18) O(2)-Cr(1)-N(1) 173.2(2) O(1)-Cr(1)-N(1) 91.3(2) O(2)-Cr(1)-N(2) 91.7(2) O(1)-Cr(1)-N(2) 172.4(2) N(1)-Cr(1)-N(2) 82.4(2) O(2)-Cr(1)-O(3) 87.69(19) O(1)-Cr(1)-O(3) 88.47(19) N(1)-Cr(1)-O(3) 88.5(2) N(2)-Cr(1)-O(3) 87.1(2) O(2)-Cr(1)-Br(1) 92.06(15) O(1)-Cr(1)-Br(1) 95.88(15) N(1)-Cr(1)-Br(1) 91.31(16) N(2)-Cr(1)-Br(1) 88.59(16) O(3)-Cr(1)-Br(1) 175.65(13)
222
C(2)-N(1)-C(1) 122.9(6) C(2)-N(1)-Cr(1) 124.2(5) C(1)-N(1)-Cr(1) 112.8(4) C(18)-N(2)-C(17) 123.4(5) C(18)-N(2)-Cr(1) 123.6(4) C(17)-N(2)-Cr(1) 112.9(4) C(4)-O(1)-Cr(1) 130.8(4) C(20)-O(2)-Cr(1) 130.9(4) C(37)-O(3)-C(40) 108.0(6) C(37)-O(3)-Cr(1) 127.3(5) C(40)-O(3)-Cr(1) 122.9(5) C(36)-C(1)-C(17) 119.4(6) C(36)-C(1)-N(1) 124.4(6) C(17)-C(1)-N(1) 116.2(6) N(1)-C(2)-C(3) 128.1(6) C(8)-C(3)-C(4) 119.2(6) C(8)-C(3)-C(2) 117.4(6) C(4)-C(3)-C(2) 123.3(6) O(1)-C(4)-C(3) 122.2(6) O(1)-C(4)-C(5) 120.1(6) C(3)-C(4)-C(5) 117.7(6) C(6)-C(5)-C(4) 118.3(6) C(6)-C(5)-C(13) 122.6(6) C(4)-C(5)-C(13) 119.1(6) C(5)-C(6)-C(7) 125.6(6) C(8)-C(7)-C(6) 115.4(6) C(8)-C(7)-C(9) 124.1(6) C(6)-C(7)-C(9) 120.5(6) C(7)-C(8)-C(3) 123.6(6) C(7)-C(9)-C(11) 111.3(6) C(7)-C(9)-C(12) 108.9(6) C(11)-C(9)-C(12) 108.1(6) C(7)-C(9)-C(10) 111.1(6) C(11)-C(9)-C(10) 107.3(6) C(12)-C(9)-C(10) 110.0(6) C(15)-C(13)-C(5) 110.4(6) C(15)-C(13)-C(14) 111.0(6) C(5)-C(13)-C(14) 109.7(6) C(15)-C(13)-C(16) 107.0(6) C(5)-C(13)-C(16) 111.2(6) C(14)-C(13)-C(16) 107.4(6) C(33)-C(17)-C(1) 120.2(6) C(33)-C(17)-N(2) 124.2(6) C(1)-C(17)-N(2) 115.5(5)
N(2)-C(18)-C(19) 127.8(6) C(20)-C(19)-C(24) 119.3(6) C(20)-C(19)-C(18) 123.9(6) C(24)-C(19)-C(18) 116.8(6) O(2)-C(20)-C(21) 121.1(6) O(2)-C(20)-C(19) 120.9(6) C(21)-C(20)-C(19) 118.1(6) C(22)-C(21)-C(20) 118.9(6) C(22)-C(21)-C(29) 120.9(6) C(20)-C(21)-C(29) 120.3(5) C(21)-C(22)-C(23) 124.7(6) C(24)-C(23)-C(22) 116.0(6) C(24)-C(23)-C(25) 120.4(6) C(22)-C(23)-C(25) 123.6(6) C(23)-C(24)-C(19) 122.8(6) C(23)-C(25)-C(28) 111.6(6) C(23)-C(25)-C(27) 109.1(6) C(28)-C(25)-C(27) 108.5(6) C(23)-C(25)-C(26) 109.8(5) C(28)-C(25)-C(26) 108.2(6) C(27)-C(25)-C(26) 109.6(6) C(31)-C(29)-C(30) 106.9(6) C(31)-C(29)-C(32) 110.8(6) C(30)-C(29)-C(32) 107.9(6) C(31)-C(29)-C(21) 109.5(6) C(30)-C(29)-C(21) 112.4(6) C(32)-C(29)-C(21) 109.3(6) C(34)-C(33)-C(17) 119.2(6) C(33)-C(34)-C(35) 121.1(6) C(36)-C(35)-C(34) 119.5(6) C(1)-C(36)-C(35) 120.5(6) O(3)-C(37)-C(38) 106.2(7) C(39)-C(38)-C(37) 103.8(7) C(40)-C(39)-C(38) 106.7(8) C(39)-C(40)-O(3) 109.5(7) C(2S)-C(1S)-O(1S) 113.2(15) C(1S)-C(2S)-C(3S) 112(2) C(2S)-C(3S)-C(4S) 103.6(16) C(3S)-C(4S)-O(1S) 106.0(14) O(2S)-C(5S)-C(6S) 107.9(11) C(5S)-C(6S)-C(7S) 99.4(10) C(8S)-C(7S)-C(6S) 109.7(14) C(7S)-C(8S)-O(2S) 104.9(13) C(10S)-C(9S)-O(3S) 101.3(8)
223
C(9S)-C(10S)-C(11S) 111.1(9) C(12S)-C(11S)-C(10S) 106.5(8) O(3S)-C(12S)-C(11S) 108.1(6)
C(1S)-O(1S)-C(4S) 96.6(12) C(5S)-O(2S)-C(8S) 108.3(11) C(12S)-O(3S)-C(9S) 106.1(7)
_______________________________________________________________________ Table C.3. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 2.CH3CN. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Cr(1) 9291(1) 6999(1) 10077(1) 16(1) N(1) 9326(4) 5998(4) 9520(3) 16(2) N(2) 7986(4) 6711(4) 10030(3) 17(2) N(3) 8907(4) 7484(4) 8994(4) 17(2) O(1) 10520(3) 7210(3) 9985(3) 20(1) O(2) 9110(4) 7965(3) 10565(3) 17(1) Br(1) 9625(1) 6350(1) 11293(1) 49(1) C(1) 8480(5) 5594(5) 9408(4) 18(2) C(2) 10028(6) 5725(5) 9243(4) 20(2) C(3) 10884(5) 6090(5) 9288(4) 18(2) C(4) 11103(6) 6812(5) 9657(4) 20(2) C(5) 11987(5) 7107(4) 9666(4) 15(2) C(6) 12585(5) 6690(5) 9290(4) 20(2) C(7) 12381(6) 5985(5) 8910(4) 20(2) C(8) 11538(5) 5700(5) 8928(4) 18(2) C(9) 13067(6) 5610(5) 8458(5) 24(2) C(10) 12792(6) 4768(5) 8242(5) 33(2) C(11) 14001(6) 5574(5) 8927(5) 30(2) C(12) 13090(7) 6074(6) 7734(5) 38(2) C(13) 12258(5) 7854(4) 10089(5) 19(2) C(14) 11684(6) 8535(5) 9743(5) 27(2) C(15) 12158(6) 7763(5) 10939(5) 29(2) C(16) 13237(6) 8078(5) 10051(5) 30(2) C(17) 7768(5) 5993(4) 9676(4) 15(2) C(18) 7384(6) 7145(5) 10284(4) 21(2) C(19) 7537(6) 7872(4) 10666(4) 18(2) C(20) 8399(6) 8229(4) 10831(4) 18(2) C(21) 8459(5) 8910(5) 11280(4) 18(2) C(22) 7676(5) 9233(5) 11482(5) 23(2) C(23) 6807(6) 8912(5) 11278(5) 25(2) C(24) 6775(6) 8225(5) 10891(5) 25(2)
224
C(25) 5988(6) 9347(5) 11469(6) 35(2) C(26) 6087(7) 9516(7) 12319(6) 52(3) C(27) 5143(7) 8876(6) 11262(7) 48(3) C(28) 5895(7) 10117(6) 11030(7) 49(3) C(29) 9383(5) 9308(5) 11543(5) 20(2) C(30) 9302(6) 9989(5) 12055(5) 25(2) C(31) 9790(6) 9575(5) 10840(5) 24(2) C(32) 10002(6) 8716(5) 11989(5) 25(2) C(33) 6923(6) 5660(5) 9584(4) 22(2) C(34) 6785(6) 4938(5) 9249(5) 21(2) C(35) 7498(6) 4550(5) 8999(4) 22(2) C(36) 8347(6) 4874(5) 9080(4) 19(2) C(37) 8597(7) 7596(6) 8399(7) 46(3) C(38) 8217(7) 7771(6) 7622(5) 38(3) C(1S) 6381(14) 7363(9) 8488(10) 140(9) C(2S) 6060(20) 7920(30) 8658(14) 630(70) C(3S) 2185(8) 6870(6) 2803(5) 35(2) C(4S) 2853(8) 6601(6) 2831(6) 45(3) C(5S) 3787(10) 642(11) 1552(9) 106(6) C(6S) 3124(10) 748(12) 1141(8) 101(6) C(7S) 5023(7) 6582(6) 1239(7) 37(3) C(8S) 4713(9) 6621(7) 1990(6) 63(4) N(1S) 5055(14) 7787(12) 9020(10) 164(7) N(2S) 1303(7) 7241(6) 2760(6) 63(3) N(3S) 2359(10) 577(7) 657(8) 117(5) N(4S) 5247(6) 6551(5) 664(6) 46(2) _______________________________________________________________________ Table C.4. Bond lengths [Å] and angles [°] for 2.CH3CN. _______________________________________________________________________ Cr(1)-O(1) 1.913(5) Cr(1)-O(2) 1.924(5) Cr(1)-N(1) 2.004(6) Cr(1)-N(2) 2.015(7) Cr(1)-N(3) 2.100(7) Cr(1)-Br(1) 2.4191(18) N(1)-C(2) 1.313(10) N(1)-C(1) 1.441(10) N(2)-C(18) 1.305(10) N(2)-C(17) 1.415(10) N(3)-C(37) 1.108(13) O(1)-C(4) 1.313(10) O(2)-C(20) 1.309(9)
C(1)-C(36) 1.382(11) C(1)-C(17) 1.412(11) C(2)-C(3) 1.428(11) C(3)-C(8) 1.415(11) C(3)-C(4) 1.432(11) C(4)-C(5) 1.423(11) C(5)-C(6) 1.393(11) C(5)-C(13) 1.526(11) C(6)-C(7) 1.411(12) C(7)-C(8) 1.366(11) C(7)-C(9) 1.533(11) C(9)-C(12) 1.519(12) C(9)-C(11) 1.531(12)
225
C(9)-C(10) 1.553(12) C(13)-C(16) 1.532(11) C(13)-C(14) 1.541(11) C(13)-C(15) 1.540(11) C(17)-C(33) 1.384(11) C(18)-C(19) 1.435(11) C(19)-C(24) 1.405(12) C(19)-C(20) 1.430(12) C(20)-C(21) 1.422(11) C(21)-C(22) 1.394(11) C(21)-C(29) 1.564(11) C(22)-C(23) 1.421(12) C(23)-C(24) 1.373(12) C(23)-C(25) 1.522(12) C(25)-C(26) 1.521(13) C(25)-C(27) 1.512(13) C(25)-C(28) 1.543(14) C(29)-C(30) 1.506(11) C(29)-C(32) 1.531(11) C(29)-C(31) 1.531(12) C(33)-C(34) 1.390(11) C(34)-C(35) 1.387(12) C(35)-C(36) 1.385(11) C(37)-C(38) 1.447(16) C(1S)-C(2S) 1.135(19) C(2S)-N(1S) 1.74(5) C(3S)-C(4S) 1.102(13) C(3S)-N(2S) 1.466(15) C(5S)-C(6S) 1.166(14) C(6S)-N(3S) 1.369(18) C(7S)-N(4S) 1.116(13) C(7S)-C(8S) 1.469(17) O(1)-Cr(1)-O(2) 93.9(2) O(1)-Cr(1)-N(1) 91.9(2) O(2)-Cr(1)-N(1) 173.3(2) O(1)-Cr(1)-N(2) 172.1(2) O(2)-Cr(1)-N(2) 92.2(2) N(1)-Cr(1)-N(2) 81.7(3) O(1)-Cr(1)-N(3) 89.6(2) O(2)-Cr(1)-N(3) 91.2(2) N(1)-Cr(1)-N(3) 85.5(2) N(2)-Cr(1)-N(3) 85.3(3) O(1)-Cr(1)-Br(1) 94.59(17)
O(2)-Cr(1)-Br(1) 91.91(16) N(1)-Cr(1)-Br(1) 90.92(18) N(2)-Cr(1)-Br(1) 90.18(18) N(3)-Cr(1)-Br(1) 174.62(18) C(2)-N(1)-C(1) 120.8(7) C(2)-N(1)-Cr(1) 125.1(6) C(1)-N(1)-Cr(1) 114.1(5) C(18)-N(2)-C(17) 122.2(7) C(18)-N(2)-Cr(1) 124.0(5) C(17)-N(2)-Cr(1) 113.7(5) C(37)-N(3)-Cr(1) 164.6(8) C(4)-O(1)-Cr(1) 130.4(5) C(20)-O(2)-Cr(1) 129.8(5) C(36)-C(1)-C(17) 120.8(7) C(36)-C(1)-N(1) 124.9(7) C(17)-C(1)-N(1) 114.2(7) N(1)-C(2)-C(3) 125.7(8) C(8)-C(3)-C(4) 119.7(7) C(8)-C(3)-C(2) 116.0(7) C(4)-C(3)-C(2) 124.3(7) O(1)-C(4)-C(3) 122.6(7) O(1)-C(4)-C(5) 119.0(7) C(3)-C(4)-C(5) 118.4(7) C(6)-C(5)-C(4) 118.0(7) C(6)-C(5)-C(13) 122.1(7) C(4)-C(5)-C(13) 119.9(7) C(5)-C(6)-C(7) 124.6(8) C(8)-C(7)-C(6) 116.4(7) C(8)-C(7)-C(9) 123.4(7) C(6)-C(7)-C(9) 120.0(7) C(7)-C(8)-C(3) 122.8(7) C(12)-C(9)-C(11) 110.6(7) C(12)-C(9)-C(7) 108.0(7) C(11)-C(9)-C(7) 111.6(7) C(12)-C(9)-C(10) 109.2(7) C(11)-C(9)-C(10) 106.7(7) C(7)-C(9)-C(10) 110.7(7) C(5)-C(13)-C(16) 112.8(7) C(5)-C(13)-C(14) 111.2(6) C(16)-C(13)-C(14) 106.1(7) C(5)-C(13)-C(15) 109.6(7) C(16)-C(13)-C(15) 107.0(7) C(14)-C(13)-C(15) 110.0(7) C(33)-C(17)-N(2) 125.1(7)
226
C(33)-C(17)-C(1) 118.8(7) N(2)-C(17)-C(1) 116.2(7) N(2)-C(18)-C(19) 126.7(8) C(24)-C(19)-C(20) 120.2(7) C(24)-C(19)-C(18) 115.7(7) C(20)-C(19)-C(18) 124.0(7) O(2)-C(20)-C(21) 120.0(7) O(2)-C(20)-C(19) 122.4(7) C(21)-C(20)-C(19) 117.5(7) C(20)-C(21)-C(22) 119.1(7) C(20)-C(21)-C(29) 121.3(7) C(22)-C(21)-C(29) 119.5(7) C(21)-C(22)-C(23) 123.8(8) C(24)-C(23)-C(22) 115.9(8) C(24)-C(23)-C(25) 124.6(8) C(22)-C(23)-C(25) 119.5(7) C(23)-C(24)-C(19) 123.1(8) C(23)-C(25)-C(26) 110.0(8) C(23)-C(25)-C(27) 110.9(8)
C(26)-C(25)-C(27) 108.0(9) C(23)-C(25)-C(28) 109.8(8) C(26)-C(25)-C(28) 108.6(9) C(27)-C(25)-C(28) 109.5(8) C(30)-C(29)-C(32) 108.1(7) C(30)-C(29)-C(31) 109.0(7) C(32)-C(29)-C(31) 109.9(7) C(30)-C(29)-C(21) 112.6(7) C(32)-C(29)-C(21) 107.9(7) C(31)-C(29)-C(21) 109.3(6) C(34)-C(33)-C(17) 120.5(8) C(33)-C(34)-C(35) 119.8(8) C(34)-C(35)-C(36) 120.7(8) C(1)-C(36)-C(35) 119.3(8) N(3)-C(37)-C(38) 177.5(12) C(1S)-C(2S)-N(1S) 114(5) C(4S)-C(3S)-N(2S) 178.9(12) C(5S)-C(6S)-N(3S) 158(2) N(4S)-C(7S)-C(8S) 179.1(12)
_______________________________________________________________________ Table C.5. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 2.OPBu3. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Cr(1) 6823(1) 174(1) 1443(1) 23(1) N(1) 5800(2) -397(2) 1602(2) 23(1) N(2) 6287(2) 1056(2) 1855(2) 22(1) O(1) 7289(2) -740(2) 1114(1) 28(1) O(2) 7754(2) 814(2) 1312(2) 28(1) O(3) 7283(2) -175(2) 2222(2) 31(1) O(4) 6257(2) 455(2) 683(1) 29(1) P(1) 7354(1) -223(1) 2870(1) 37(1) P(2) 6070(1) 1075(1) 231(1) 28(1) C(1) 5224(3) 94(3) 1865(2) 24(1) C(2) 5662(3) -1135(3) 1475(2) 24(1) C(3) 6220(3) -1669(3) 1230(2) 24(1) C(4) 7013(3) -1459(3) 1078(2) 26(1) C(5) 7529(3) -2064(3) 866(2) 29(1)
227
C(6) 7205(3) -2798(3) 779(2) 31(1) C(7) 6405(3) -3013(3) 891(2) 30(1) C(8) 5937(3) -2442(3) 1124(2) 28(1) C(9) 6094(4) -3845(3) 725(2) 35(1) C(10) 5227(4) -3963(3) 885(3) 44(2) C(11) 6130(4) -3942(4) 60(3) 54(2) C(12) 6634(4) -4469(3) 1033(3) 43(2) C(13) 8409(3) -1877(3) 750(2) 35(1) C(14) 8466(4) -1239(3) 281(2) 40(2) C(15) 8862(4) -1593(4) 1313(3) 43(2) C(16) 8866(4) -2588(4) 528(3) 51(2) C(17) 5501(3) 859(3) 2019(2) 24(1) C(18) 6642(3) 1720(3) 2004(2) 24(1) C(19) 7424(3) 1970(3) 1844(2) 26(1) C(20) 7952(3) 1511(3) 1509(2) 25(1) C(21) 8725(3) 1846(3) 1386(2) 27(1) C(22) 8885(3) 2598(3) 1570(2) 29(1) C(23) 8364(3) 3072(3) 1879(2) 29(1) C(24) 7661(3) 2744(3) 2021(2) 27(1) C(25) 8622(3) 3909(3) 2053(3) 38(2) C(26) 8843(4) 4363(4) 1504(3) 62(2) C(27) 7925(4) 4357(3) 2312(3) 42(2) C(28) 9351(4) 3900(4) 2476(3) 62(2) C(29) 9337(3) 1346(3) 1071(2) 33(1) C(30) 9538(4) 593(4) 1410(3) 48(2) C(31) 10130(3) 1799(4) 1011(3) 45(2) C(32) 8999(4) 1143(4) 458(2) 42(2) C(33) 4439(3) -128(3) 1985(2) 27(1) C(34) 3951(3) 391(3) 2263(2) 27(1) C(35) 4231(3) 1124(3) 2429(2) 25(1) C(36) 4998(3) 1361(3) 2312(2) 24(1) C(37) 7860(4) 621(4) 3190(3) 47(2) C(38) 8682(4) 780(4) 2971(3) 56(2) C(39) 9025(5) 1563(5) 3237(5) 102(3) C(40) 9814(8) 1707(6) 3026(5) 143(5) C(41) 6410(4) -255(3) 3225(3) 42(2) C(42) 5859(4) -970(3) 3127(2) 38(1) C(43) 5070(3) -893(3) 3419(2) 37(1) C(44) 4509(4) -1579(3) 3294(3) 46(2) C(45) 7933(4) -1091(3) 3070(3) 42(2) C(46) 7713(4) -1830(3) 2713(3) 43(2) C(47) 8317(4) -2483(3) 2834(3) 46(2) C(48) 8082(4) -3233(4) 2507(3) 55(2) C(49) 6565(4) 1989(3) 416(2) 36(1)
228
C(50) 6368(4) 2680(3) 20(3) 50(2) C(51) 6902(6) 3379(4) 139(3) 80(3) C(52) 7672(8) 3301(8) 15(7) 200(8) C(53) 6370(3) 764(3) -470(2) 30(1) C(54) 7272(3) 609(3) -495(2) 37(1) C(55) 7509(4) 283(4) -1071(2) 41(2) C(56) 8403(4) 165(4) -1099(3) 55(2) C(57) 5007(3) 1254(3) 118(2) 33(1) C(58) 4560(3) 1556(3) 637(2) 36(1) C(59) 3665(3) 1676(3) 490(2) 33(1) C(60) 3222(4) 2035(4) 979(3) 43(2) Br(1) 6284(1) 2707(1) 3342(1) 37(1) C(1S) 9745(15) 5183(18) 10012(8) 268(14) C(2S) 9199(10) 5486(11) 9557(6) 171(7) C(3S) 8570(30) 5482(13) 9763(13) 520(40) _______________________________________________________________________ Table C.6. Bond lengths [Å] and angles [°] for 2.OPBu3. _______________________________________________________________________ Cr(1)-O(1) 1.910(3) Cr(1)-O(2) 1.925(3) Cr(1)-N(1) 2.004(4) Cr(1)-O(3) 2.005(3) Cr(1)-O(4) 2.003(3) Cr(1)-N(2) 2.008(4) N(1)-C(2) 1.305(6) N(1)-C(1) 1.428(6) N(2)-C(18) 1.309(6) N(2)-C(17) 1.417(6) O(1)-C(4) 1.306(6) O(2)-C(20) 1.304(6) O(3)-P(1) 1.495(4) O(4)-P(2) 1.504(4) P(1)-C(37) 1.801(6) P(1)-C(45) 1.806(6) P(1)-C(41) 1.806(6) P(2)-C(53) 1.796(5) P(2)-C(57) 1.794(6) P(2)-C(49) 1.797(6) C(1)-C(33) 1.396(7) C(1)-C(17) 1.419(7) C(2)-C(3) 1.434(7) C(3)-C(4) 1.424(7)
C(3)-C(8) 1.412(7) C(4)-C(5) 1.439(7) C(5)-C(6) 1.369(7) C(5)-C(13) 1.530(8) C(6)-C(7) 1.412(8) C(7)-C(8) 1.371(7) C(7)-C(9) 1.547(7) C(9)-C(10) 1.516(8) C(9)-C(12) 1.537(8) C(9)-C(11) 1.548(8) C(13)-C(14) 1.538(8) C(13)-C(16) 1.529(8) C(13)-C(15) 1.542(8) C(17)-C(36) 1.392(7) C(18)-C(19) 1.431(7) C(19)-C(20) 1.431(7) C(19)-C(24) 1.425(7) C(20)-C(21) 1.443(7) C(21)-C(22) 1.369(7) C(21)-C(29) 1.535(7) C(22)-C(23) 1.403(7) C(23)-C(24) 1.348(7) C(23)-C(25) 1.534(7) C(25)-C(28) 1.513(9)
229
C(25)-C(27) 1.532(8) C(25)-C(26) 1.544(9) C(29)-C(32) 1.534(8) C(29)-C(30) 1.527(8) C(29)-C(31) 1.536(8) C(33)-C(34) 1.377(7) C(34)-C(35) 1.378(7) C(35)-C(36) 1.374(7) C(37)-C(38) 1.504(9) C(38)-C(39) 1.560(10) C(39)-C(40) 1.441(14) C(41)-C(42) 1.529(8) C(42)-C(43) 1.508(8) C(43)-C(44) 1.509(8) C(45)-C(46) 1.535(8) C(46)-C(47) 1.511(8) C(47)-C(48) 1.521(9) C(49)-C(50) 1.514(8) C(50)-C(51) 1.498(9) C(51)-C(52) 1.330(15) C(53)-C(54) 1.522(7) C(54)-C(55) 1.511(8) C(55)-C(56) 1.500(8) C(57)-C(58) 1.529(7) C(58)-C(59) 1.518(7) C(59)-C(60) 1.509(7) C(1S)-C(1S)#1 1.05(3) C(1S)-C(2S) 1.444(19) C(1S)-C(3S) 2.06(5) C(2S)-C(3S) 1.17(3) O(1)-Cr(1)-O(2) 93.05(15) O(1)-Cr(1)-N(1) 92.43(15) O(2)-Cr(1)-N(1) 174.46(16) O(1)-Cr(1)-O(3) 88.46(14) O(2)-Cr(1)-O(3) 92.24(15) N(1)-Cr(1)-O(3) 88.70(15) O(1)-Cr(1)-O(4) 91.50(14) O(2)-Cr(1)-O(4) 93.97(15) N(1)-Cr(1)-O(4) 85.09(15) O(3)-Cr(1)-O(4) 173.78(15) O(1)-Cr(1)-N(2) 173.73(16) O(2)-Cr(1)-N(2) 91.74(15) N(1)-Cr(1)-N(2) 82.86(16)
O(3)-Cr(1)-N(2) 87.31(15) O(4)-Cr(1)-N(2) 92.21(15) C(2)-N(1)-C(1) 122.9(4) C(2)-N(1)-Cr(1) 124.4(4) C(1)-N(1)-Cr(1) 112.7(3) C(18)-N(2)-C(17) 122.7(4) C(18)-N(2)-Cr(1) 124.3(3) C(17)-N(2)-Cr(1) 112.8(3) C(4)-O(1)-Cr(1) 129.7(3) C(20)-O(2)-Cr(1) 130.4(3) P(1)-O(3)-Cr(1) 156.8(2) P(2)-O(4)-Cr(1) 147.6(2) O(3)-P(1)-C(37) 112.2(3) O(3)-P(1)-C(45) 108.3(2) C(37)-P(1)-C(45) 108.5(3) O(3)-P(1)-C(41) 115.5(3) C(37)-P(1)-C(41) 103.4(3) C(45)-P(1)-C(41) 108.7(3) O(4)-P(2)-C(53) 111.2(2) O(4)-P(2)-C(57) 112.6(2) C(53)-P(2)-C(57) 103.7(2) O(4)-P(2)-C(49) 111.5(2) C(53)-P(2)-C(49) 108.9(3) C(57)-P(2)-C(49) 108.7(3) C(33)-C(1)-C(17) 119.3(5) C(33)-C(1)-N(1) 125.3(4) C(17)-C(1)-N(1) 115.3(4) N(1)-C(2)-C(3) 126.0(5) C(4)-C(3)-C(8) 119.6(5) C(4)-C(3)-C(2) 124.2(4) C(8)-C(3)-C(2) 116.2(5) O(1)-C(4)-C(3) 122.9(5) O(1)-C(4)-C(5) 118.6(5) C(3)-C(4)-C(5) 118.5(5) C(6)-C(5)-C(4) 117.8(5) C(6)-C(5)-C(13) 122.3(5) C(4)-C(5)-C(13) 120.0(5) C(5)-C(6)-C(7) 125.1(5) C(8)-C(7)-C(6) 116.4(5) C(8)-C(7)-C(9) 123.9(5) C(6)-C(7)-C(9) 119.7(5) C(7)-C(8)-C(3) 122.5(5) C(10)-C(9)-C(7) 111.5(5) C(10)-C(9)-C(12) 109.5(5)
230
C(7)-C(9)-C(12) 109.8(5) C(10)-C(9)-C(11) 108.3(5) C(7)-C(9)-C(11) 108.2(5) C(12)-C(9)-C(11) 109.4(5) C(5)-C(13)-C(14) 111.3(5) C(5)-C(13)-C(16) 112.8(5) C(14)-C(13)-C(16) 105.8(5) C(5)-C(13)-C(15) 110.1(5) C(14)-C(13)-C(15) 109.1(5) C(16)-C(13)-C(15) 107.5(5) C(36)-C(17)-N(2) 124.6(4) C(36)-C(17)-C(1) 119.3(5) N(2)-C(17)-C(1) 116.1(4) N(2)-C(18)-C(19) 126.1(5) C(20)-C(19)-C(24) 119.4(5) C(20)-C(19)-C(18) 124.4(5) C(24)-C(19)-C(18) 116.1(4) O(2)-C(20)-C(19) 122.3(4) O(2)-C(20)-C(21) 119.9(4) C(19)-C(20)-C(21) 117.7(4) C(22)-C(21)-C(20) 117.8(5) C(22)-C(21)-C(29) 122.8(5) C(20)-C(21)-C(29) 119.4(4) C(21)-C(22)-C(23) 125.4(5) C(24)-C(23)-C(22) 116.7(5) C(24)-C(23)-C(25) 123.6(5) C(22)-C(23)-C(25) 119.7(5) C(23)-C(24)-C(19) 122.7(5) C(23)-C(25)-C(28) 111.2(5) C(23)-C(25)-C(27) 111.0(5) C(28)-C(25)-C(27) 110.3(5) C(23)-C(25)-C(26) 108.9(5) C(28)-C(25)-C(26) 108.6(5) C(27)-C(25)-C(26) 106.8(5)
C(32)-C(29)-C(30) 110.1(5) C(32)-C(29)-C(21) 110.0(4) C(30)-C(29)-C(21) 110.7(5) C(32)-C(29)-C(31) 107.5(5) C(30)-C(29)-C(31) 107.6(5) C(21)-C(29)-C(31) 110.8(4) C(1)-C(33)-C(34) 119.7(5) C(35)-C(34)-C(33) 120.8(5) C(34)-C(35)-C(36) 120.8(5) C(17)-C(36)-C(35) 120.0(5) C(38)-C(37)-P(1) 114.5(4) C(37)-C(38)-C(39) 109.8(6) C(40)-C(39)-C(38) 109.3(9) C(42)-C(41)-P(1) 118.7(4) C(41)-C(42)-C(43) 112.9(5) C(44)-C(43)-C(42) 112.8(5) C(46)-C(45)-P(1) 115.0(4) C(47)-C(46)-C(45) 111.4(5) C(46)-C(47)-C(48) 112.0(5) C(50)-C(49)-P(2) 116.6(4) C(51)-C(50)-C(49) 113.6(6) C(52)-C(51)-C(50) 116.4(10) C(54)-C(53)-P(2) 113.9(4) C(55)-C(54)-C(53) 113.6(5) C(56)-C(55)-C(54) 113.0(5) C(58)-C(57)-P(2) 117.2(4) C(57)-C(58)-C(59) 112.2(4) C(60)-C(59)-C(58) 113.3(5) C(1S)#1-C(1S)-C(2S) 130(3) C(1S)#1-C(1S)-C(3S) 151(4) C(2S)-C(1S)-C(3S) 33.3(8) C(3S)-C(2S)-C(1S) 104(3) C(2S)-C(3S)-C(1S) 43(2)
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231
Table C.7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 7a. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Cr(1A) 7401(1) 3510(1) 6665(1) 20(1) Cr(1B) 7376(1) 8472(1) 3393(1) 19(1) Cl(1A) 7488(1) 3279(1) 5698(1) 30(1) Cl(1B) 7465(1) 8805(1) 4362(1) 27(1) N(1A) 7552(4) 2517(5) 6829(4) 23(2) N(2A) 8345(4) 3671(4) 6830(4) 20(2) N(3A) 6471(4) 3357(4) 6530(4) 19(2) N(1B) 7409(4) 9462(4) 3188(4) 23(2) N(2B) 8321(4) 8424(5) 3474(3) 19(2) N(3B) 6436(4) 8517(4) 3297(4) 15(2) O(1A) 7254(3) 4409(3) 6526(3) 21(2) O(2A) 7337(3) 3667(3) 7487(3) 23(2) O(1B) 7342(3) 7580(3) 3574(3) 21(2) O(2B) 7316(3) 8238(3) 2571(3) 18(2) C(1A) 7699(5) 2004(6) 6871(5) 32(3) C(2A) 7901(5) 1330(5) 6942(5) 53(4) C(3A) 8580(5) 4236(6) 6834(4) 27(3) C(4A) 8259(5) 4851(5) 6710(5) 23(3) C(5A) 8638(5) 5400(6) 6726(5) 42(4) C(6A) 8382(5) 6013(5) 6603(5) 32(3) C(7A) 7779(5) 6054(5) 6471(5) 26(3) C(8A) 7375(5) 5532(6) 6443(5) 24(3) C(9A) 7623(5) 4914(6) 6569(5) 22(3) C(10A) 8783(5) 3133(5) 6871(5) 22(3) C(11A) 8899(5) 2786(6) 7391(4) 24(3) C(12A) 9263(5) 2232(5) 7406(5) 30(3) C(13A) 9499(6) 2063(7) 6911(5) 55(4) C(14A) 9419(5) 2437(6) 6396(5) 39(4) C(15A) 9052(5) 2972(6) 6366(5) 32(3) C(16A) 9021(5) 3424(6) 5832(5) 34(3) C(17A) 8927(5) 3050(6) 5248(5) 45(4) C(18A) 9613(5) 3830(6) 5880(5) 48(4) C(19A) 8701(5) 3016(5) 7962(5) 30(3) C(20A) 8309(5) 2517(6) 8238(5) 42(4) C(21A) 9271(5) 3187(6) 8418(5) 47(4) C(22A) 6722(5) 5664(5) 6318(5) 25(3) C(23A) 6334(5) 5450(5) 6720(5) 21(3)
232
C(24A) 5734(5) 5634(5) 6647(5) 24(3) C(25A) 5508(5) 6011(5) 6176(5) 27(3) C(26A) 5861(5) 6213(5) 5761(5) 30(3) C(27A) 6470(5) 6033(5) 5851(5) 26(3) C(28A) 6103(5) 3602(5) 6866(5) 26(3) C(29A) 6291(5) 3957(5) 7395(5) 20(3) C(30A) 5831(5) 4262(5) 7644(5) 30(3) C(31A) 5967(5) 4621(5) 8157(5) 28(3) C(32A) 6543(5) 4687(5) 8426(5) 28(3) C(33A) 7026(5) 4362(6) 8208(5) 27(2) C(34A) 6908(5) 3998(6) 7683(5) 27(2) C(35A) 6152(5) 2995(6) 6038(5) 20(3) C(36A) 5973(5) 3312(6) 5485(5) 27(3) C(37A) 5666(5) 2976(6) 5010(5) 27(3) C(38A) 5551(5) 2304(6) 5088(5) 33(3) C(39A) 5717(5) 1994(6) 5632(5) 32(3) C(40A) 6023(5) 2346(5) 6115(5) 21(3) C(41A) 6131(5) 2014(5) 6718(5) 23(3) C(42A) 6312(5) 1325(5) 6662(5) 46(4) C(43A) 5546(5) 2025(5) 7001(4) 37(3) C(44A) 6099(5) 4029(5) 5422(5) 30(3) C(45A) 6340(5) 4180(6) 4847(5) 46(4) C(46A) 5526(5) 4417(5) 5454(5) 36(3) C(47A) 7649(5) 4431(5) 8525(6) 32(3) C(48A) 8115(5) 4618(5) 8214(5) 25(3) C(49A) 8705(6) 4712(5) 8525(6) 37(3) C(50A) 8791(6) 4651(5) 9127(5) 31(3) C(51A) 8337(5) 4483(5) 9423(5) 32(3) C(52A) 7780(5) 4354(5) 9128(5) 29(3) C(1B) 7499(5) 9985(6) 3158(5) 29(3) C(2B) 7654(5) 10679(5) 3096(5) 38(4) C(3B) 8609(5) 7877(6) 3496(4) 27(3) C(4B) 8353(5) 7241(5) 3520(5) 22(3) C(5B) 8773(5) 6725(6) 3507(5) 33(3) C(6B) 8595(5) 6104(6) 3541(5) 35(3) C(7B) 7996(5) 5974(6) 3555(5) 29(3) C(8B) 7545(5) 6461(6) 3552(5) 26(3) C(9B) 7746(5) 7108(5) 3547(5) 22(3) C(10B) 8721(5) 8993(5) 3514(5) 21(3) C(11B) 8785(4) 9312(5) 3000(5) 22(3) C(12B) 9123(5) 9893(5) 3051(5) 27(3) C(13B) 9372(5) 10119(5) 3611(5) 30(3) C(14B) 9326(5) 9760(6) 4107(5) 29(3) C(15B) 9005(5) 9201(5) 4074(5) 18(3)
233
C(16B) 9019(5) 8791(6) 4620(5) 31(3) C(17B) 8903(5) 9166(5) 5165(5) 37(3) C(18B) 9622(4) 8436(6) 4757(5) 38(3) C(19B) 8555(5) 9049(6) 2387(5) 29(3) C(20B) 9095(5) 8862(6) 2075(5) 45(4) C(21B) 8166(4) 9517(6) 1987(5) 38(4) C(22B) 6913(5) 6273(5) 3544(5) 25(3) C(23B) 6727(5) 5908(5) 3987(5) 32(3) C(24B) 6146(5) 5664(5) 3948(5) 29(3) C(25B) 5738(5) 5826(5) 3456(5) 32(3) C(26B) 5904(5) 6209(5) 3025(5) 30(3) C(27B) 6483(5) 6434(5) 3055(5) 23(3) C(28B) 6103(5) 8237(5) 2843(5) 20(3) C(29B) 6283(5) 7901(5) 2367(5) 27(3) C(30B) 5823(5) 7567(5) 1991(5) 25(3) C(31B) 5954(5) 7233(6) 1504(5) 36(4) C(32B) 6548(5) 7237(5) 1391(5) 25(3) C(33B) 7017(5) 7554(5) 1740(5) 21(3) C(34B) 6898(5) 7891(5) 2251(5) 25(3) C(35B) 6081(4) 8830(5) 3669(5) 14(3) C(36B) 5971(4) 8532(5) 4199(5) 22(3) C(37B) 5611(4) 8831(5) 4560(5) 20(3) C(38B) 5331(5) 9398(5) 4392(5) 26(3) C(39B) 5428(4) 9718(5) 3885(5) 25(3) C(40B) 5810(5) 9429(6) 3518(5) 22(3) C(41B) 5868(5) 9762(5) 2940(5) 29(3) C(42B) 6027(5) 10503(5) 3028(5) 40(4) C(43B) 5274(5) 9708(5) 2500(5) 30(3) C(44B) 6237(5) 7846(5) 4354(5) 23(3) C(45B) 6437(5) 7757(5) 5019(4) 29(3) C(46B) 5770(4) 7346(5) 4121(5) 34(3) C(47B) 7637(5) 7515(5) 1597(5) 27(3) C(48B) 7738(5) 7648(6) 1017(5) 34(4) C(49B) 8295(5) 7561(6) 863(5) 35(3) C(50B) 8777(5) 7347(5) 1264(5) 34(3) C(51B) 8701(5) 7208(5) 1866(5) 34(3) C(52B) 8127(5) 7293(5) 2001(5) 29(3) C(1S) 9187(11) 6900(14) 5452(12) 250(30) C(2S) 9122(12) 7412(13) 6099(10) 150(30) C(3S) 8614(14) 7733(13) 6183(11) 210(20) C(4S) 8161(13) 7670(20) 5748(18) 370(30) C(5S) 8209(14) 7290(20) 5303(16) 270(30) C(6S) 8648(13) 6974(13) 5220(9) 300(20) C(7S) 9700(10) 6614(12) 5633(14) 330(20)
234
C(8S) 8464(7) 4788(7) 4729(6) 81(3) C(9S) 9062(7) 4941(7) 4656(6) 80(3) C(10S) 9316(8) 4615(6) 4183(6) 80(3) C(11S) 8946(7) 4215(7) 3798(7) 77(3) C(12S) 8352(7) 4109(7) 3885(6) 77(3) C(13S) 8103(7) 4412(6) 4333(6) 79(3) C(14S) 8190(7) 5110(6) 5191(5) 95(4) C(15S) 7151(7) 995(9) 4926(8) 170(6) C(16S) 7569(8) 582(7) 4692(8) 168(6) C(17S) 8166(8) 730(8) 4833(8) 174(6) C(18S) 8410(7) 1199(8) 5187(7) 171(6) C(19S) 7977(8) 1619(8) 5430(8) 168(6) C(20S) 7372(7) 1510(8) 5272(8) 164(6) C(21S) 6546(7) 863(9) 4756(9) 192(8) Table C.8. Bond lengths [Å] and angles [°] for 7a. _______________________________________________________________________ Cr(1A)-O(1A) 1.916(7) Cr(1A)-O(2A) 1.948(6) Cr(1A)-N(3A) 2.082(8) Cr(1A)-N(1A) 2.113(10) Cr(1A)-N(2A) 2.115(9) Cr(1A)-Cl(1A) 2.314(3) Cr(1B)-O(1B) 1.902(7) Cr(1B)-O(2B) 1.940(7) Cr(1B)-N(3B) 2.085(8) Cr(1B)-N(2B) 2.096(8) Cr(1B)-N(1B) 2.113(9) Cr(1B)-Cl(1B) 2.316(3) N(1A)-C(1A) 1.116(13) N(2A)-C(3A) 1.286(12) N(2A)-C(10A) 1.480(12) N(3A)-C(28A) 1.316(11) N(3A)-C(35A) 1.455(12) N(1B)-C(1B) 1.108(12) N(2B)-C(3B) 1.303(12) N(2B)-C(10B) 1.477(12) N(3B)-C(28B) 1.323(12) N(3B)-C(35B) 1.410(11) O(1A)-C(9A) 1.330(12) O(2A)-C(34A) 1.312(12) O(1B)-C(9B) 1.341(11) O(2B)-C(34B) 1.315(12)
C(1A)-C(2A) 1.471(15) C(3A)-C(4A) 1.471(14) C(4A)-C(9A) 1.417(14) C(4A)-C(5A) 1.417(14) C(5A)-C(6A) 1.408(14) C(6A)-C(7A) 1.341(13) C(7A)-C(8A) 1.406(14) C(8A)-C(9A) 1.410(14) C(8A)-C(22A) 1.473(14) C(10A)-C(11A) 1.388(13) C(10A)-C(15A) 1.427(13) C(11A)-C(12A) 1.407(14) C(11A)-C(19A) 1.527(13) C(12A)-C(13A) 1.371(13) C(13A)-C(14A) 1.407(15) C(14A)-C(15A) 1.376(14) C(15A)-C(16A) 1.541(14) C(16A)-C(17A) 1.540(14) C(16A)-C(18A) 1.560(14) C(19A)-C(20A) 1.553(13) C(19A)-C(21A) 1.566(14) C(22A)-C(27A) 1.371(14) C(22A)-C(23A) 1.431(13) C(23A)-C(24A) 1.381(13) C(24A)-C(25A) 1.372(13) C(25A)-C(26A) 1.394(13)
235
C(26A)-C(27A) 1.396(13) C(28A)-C(29A) 1.432(14) C(29A)-C(30A) 1.403(12) C(29A)-C(34A) 1.442(13) C(30A)-C(31A) 1.391(14) C(31A)-C(32A) 1.349(14) C(32A)-C(33A) 1.427(13) C(33A)-C(34A) 1.416(15) C(33A)-C(47A) 1.482(14) C(35A)-C(40A) 1.394(14) C(35A)-C(36A) 1.435(14) C(36A)-C(37A) 1.390(14) C(36A)-C(44A) 1.526(15) C(37A)-C(38A) 1.436(14) C(38A)-C(39A) 1.408(14) C(39A)-C(40A) 1.421(14) C(40A)-C(41A) 1.535(14) C(41A)-C(42A) 1.497(13) C(41A)-C(43A) 1.548(12) C(44A)-C(46A) 1.524(13) C(44A)-C(45A) 1.535(13) C(47A)-C(52A) 1.385(14) C(47A)-C(48A) 1.403(12) C(48A)-C(49A) 1.417(14) C(49A)-C(50A) 1.376(14) C(50A)-C(51A) 1.350(13) C(51A)-C(52A) 1.354(14) C(1B)-C(2B) 1.496(14) C(3B)-C(4B) 1.444(14) C(4B)-C(9B) 1.396(13) C(4B)-C(5B) 1.428(13) C(5B)-C(6B) 1.355(14) C(6B)-C(7B) 1.373(13) C(7B)-C(8B) 1.428(14) C(8B)-C(9B) 1.417(14) C(8B)-C(22B) 1.464(14) C(10B)-C(11B) 1.381(14) C(10B)-C(15B) 1.419(14) C(11B)-C(12B) 1.419(14) C(11B)-C(19B) 1.530(14) C(12B)-C(13B) 1.408(14) C(13B)-C(14B) 1.380(14) C(14B)-C(15B) 1.360(14) C(15B)-C(16B) 1.515(14)
C(16B)-C(17B) 1.532(13) C(16B)-C(18B) 1.528(13) C(19B)-C(21B) 1.521(14) C(19B)-C(20B) 1.546(12) C(22B)-C(23B) 1.383(13) C(22B)-C(27B) 1.408(14) C(23B)-C(24B) 1.385(13) C(24B)-C(25B) 1.386(14) C(25B)-C(26B) 1.366(13) C(26B)-C(27B) 1.369(13) C(28B)-C(29B) 1.410(13) C(29B)-C(30B) 1.421(14) C(29B)-C(34B) 1.440(13) C(30B)-C(31B) 1.387(13) C(31B)-C(32B) 1.391(13) C(32B)-C(33B) 1.390(14) C(33B)-C(34B) 1.428(14) C(33B)-C(47B) 1.474(13) C(35B)-C(40B) 1.403(13) C(35B)-C(36B) 1.422(13) C(36B)-C(37B) 1.388(12) C(36B)-C(44B) 1.564(14) C(37B)-C(38B) 1.362(13) C(38B)-C(39B) 1.388(13) C(39B)-C(40B) 1.422(12) C(40B)-C(41B) 1.523(13) C(41B)-C(43B) 1.550(14) C(41B)-C(42B) 1.585(14) C(44B)-C(46B) 1.514(13) C(44B)-C(45B) 1.541(13) C(47B)-C(52B) 1.404(14) C(47B)-C(48B) 1.415(13) C(48B)-C(49B) 1.358(13) C(49B)-C(50B) 1.385(15) C(50B)-C(51B) 1.451(14) C(51B)-C(52B) 1.377(13) C(1S)-C(6S) 1.254(16) C(1S)-C(7S) 1.304(16) C(1S)-C(2S) 1.852(15) C(2S)-C(3S) 1.36(2) C(3S)-C(4S) 1.319(18) C(4S)-C(5S) 1.314(19) C(5S)-C(6S) 1.222(17) C(8S)-C(13S) 1.369(15)
236
C(8S)-C(9S) 1.409(14) C(8S)-C(14S) 1.466(13) C(9S)-C(10S) 1.466(13) C(10S)-C(11S) 1.393(14) C(11S)-C(12S) 1.391(14) C(12S)-C(13S) 1.393(13) C(15S)-C(20S) 1.380(15) C(15S)-C(21S) 1.381(15) C(15S)-C(16S) 1.432(16) C(16S)-C(17S) 1.363(16) C(17S)-C(18S) 1.333(15) C(18S)-C(19S) 1.475(15) C(19S)-C(20S) 1.366(16) O(1A)-Cr(1A)-O(2A) 87.9(3) O(1A)-Cr(1A)-N(3A) 88.9(3) O(2A)-Cr(1A)-N(3A) 87.3(3) O(1A)-Cr(1A)-N(1A) 178.9(3) O(2A)-Cr(1A)-N(1A) 91.3(3) N(3A)-Cr(1A)-N(1A) 90.4(3) O(1A)-Cr(1A)-N(2A) 91.1(3) O(2A)-Cr(1A)-N(2A) 90.9(3) N(3A)-Cr(1A)-N(2A) 178.2(3) N(1A)-Cr(1A)-N(2A) 89.7(3) O(1A)-Cr(1A)-Cl(1A) 94.5(2) O(2A)-Cr(1A)-Cl(1A) 177.6(2) N(3A)-Cr(1A)-Cl(1A) 92.9(3) N(1A)-Cr(1A)-Cl(1A) 86.3(2) N(2A)-Cr(1A)-Cl(1A) 88.9(2) O(1B)-Cr(1B)-O(2B) 88.3(3) O(1B)-Cr(1B)-N(3B) 89.6(3) O(2B)-Cr(1B)-N(3B) 89.1(3) O(1B)-Cr(1B)-N(2B) 90.4(3) O(2B)-Cr(1B)-N(2B) 89.8(3) N(3B)-Cr(1B)-N(2B) 178.9(3) O(1B)-Cr(1B)-N(1B) 179.6(4) O(2B)-Cr(1B)-N(1B) 91.5(3) N(3B)-Cr(1B)-N(1B) 90.0(3) N(2B)-Cr(1B)-N(1B) 89.9(4) O(1B)-Cr(1B)-Cl(1B) 94.6(2) O(2B)-Cr(1B)-Cl(1B) 177.0(2) N(3B)-Cr(1B)-Cl(1B) 91.7(2) N(2B)-Cr(1B)-Cl(1B) 89.4(2) N(1B)-Cr(1B)-Cl(1B) 85.6(3)
C(1A)-N(1A)-Cr(1A) 169.9(10) C(3A)-N(2A)-C(10A) 115.1(9) C(3A)-N(2A)-Cr(1A) 122.7(8) C(10A)-N(2A)-Cr(1A) 121.7(7) C(28A)-N(3A)-C(35A) 112.4(9) C(28A)-N(3A)-Cr(1A) 123.5(8) C(35A)-N(3A)-Cr(1A) 124.0(6) C(1B)-N(1B)-Cr(1B) 168.4(10) C(3B)-N(2B)-C(10B) 113.8(9) C(3B)-N(2B)-Cr(1B) 122.1(8) C(10B)-N(2B)-Cr(1B) 124.0(7) C(28B)-N(3B)-C(35B) 112.3(8) C(28B)-N(3B)-Cr(1B) 120.3(7) C(35B)-N(3B)-Cr(1B) 127.4(7) C(9A)-O(1A)-Cr(1A) 131.8(7) C(34A)-O(2A)-Cr(1A) 125.8(7) C(9B)-O(1B)-Cr(1B) 130.6(6) C(34B)-O(2B)-Cr(1B) 128.7(7) N(1A)-C(1A)-C(2A) 178.5(15) N(2A)-C(3A)-C(4A) 127.2(11) C(9A)-C(4A)-C(5A) 120.5(11) C(9A)-C(4A)-C(3A) 124.6(11) C(5A)-C(4A)-C(3A) 114.8(11) C(6A)-C(5A)-C(4A) 119.8(11) C(7A)-C(6A)-C(5A) 117.9(11) C(6A)-C(7A)-C(8A) 125.4(11) C(7A)-C(8A)-C(9A) 117.5(11) C(7A)-C(8A)-C(22A) 118.4(10) C(9A)-C(8A)-C(22A) 124.0(11) O(1A)-C(9A)-C(8A) 118.7(10) O(1A)-C(9A)-C(4A) 122.4(10) C(8A)-C(9A)-C(4A) 118.8(11) C(11A)-C(10A)-C(15A) 122.3(10) C(11A)-C(10A)-N(2A) 118.9(10) C(15A)-C(10A)-N(2A) 118.7(10) C(10A)-C(11A)-C(12A) 118.6(10) C(10A)-C(11A)-C(19A) 122.6(11) C(12A)-C(11A)-C(19A) 118.5(10) C(13A)-C(12A)-C(11A) 118.8(11) C(12A)-C(13A)-C(14A) 122.9(12) C(15A)-C(14A)-C(13A) 119.2(11) C(14A)-C(15A)-C(10A) 117.9(11) C(14A)-C(15A)-C(16A) 119.2(10) C(10A)-C(15A)-C(16A) 122.3(10)
237
C(17A)-C(16A)-C(15A) 111.9(10) C(17A)-C(16A)-C(18A) 109.8(9) C(15A)-C(16A)-C(18A) 109.6(10) C(11A)-C(19A)-C(20A) 113.5(9) C(11A)-C(19A)-C(21A) 109.6(9) C(20A)-C(19A)-C(21A) 109.3(9) C(27A)-C(22A)-C(23A) 117.5(10) C(27A)-C(22A)-C(8A) 122.6(10) C(23A)-C(22A)-C(8A) 119.7(11) C(24A)-C(23A)-C(22A) 120.5(11) C(25A)-C(24A)-C(23A) 119.4(10) C(24A)-C(25A)-C(26A) 122.3(10) C(25A)-C(26A)-C(27A) 117.3(11) C(22A)-C(27A)-C(26A) 123.0(11) N(3A)-C(28A)-C(29A) 124.8(10) C(30A)-C(29A)-C(28A) 116.1(10) C(30A)-C(29A)-C(34A) 119.8(11) C(28A)-C(29A)-C(34A) 124.1(10) C(31A)-C(30A)-C(29A) 120.4(11) C(32A)-C(31A)-C(30A) 121.2(11) C(31A)-C(32A)-C(33A) 120.7(11) C(34A)-C(33A)-C(32A) 119.9(10) C(34A)-C(33A)-C(47A) 120.9(10) C(32A)-C(33A)-C(47A) 119.2(11) O(2A)-C(34A)-C(33A) 121.3(10) O(2A)-C(34A)-C(29A) 120.6(11) C(33A)-C(34A)-C(29A) 117.8(11) C(40A)-C(35A)-C(36A) 121.4(11) C(40A)-C(35A)-N(3A) 119.0(10) C(36A)-C(35A)-N(3A) 119.5(10) C(37A)-C(36A)-C(35A) 120.5(12) C(37A)-C(36A)-C(44A) 119.4(11) C(35A)-C(36A)-C(44A) 120.1(11) C(36A)-C(37A)-C(38A) 117.9(11) C(39A)-C(38A)-C(37A) 121.8(12) C(38A)-C(39A)-C(40A) 119.6(11) C(35A)-C(40A)-C(39A) 118.8(11) C(35A)-C(40A)-C(41A) 122.8(10) C(39A)-C(40A)-C(41A) 118.0(10) C(42A)-C(41A)-C(40A) 111.1(9) C(42A)-C(41A)-C(43A) 107.8(9) C(40A)-C(41A)-C(43A) 110.2(9) C(46A)-C(44A)-C(36A) 110.0(9) C(46A)-C(44A)-C(45A) 109.9(10)
C(36A)-C(44A)-C(45A) 112.1(10) C(52A)-C(47A)-C(48A) 118.8(11) C(52A)-C(47A)-C(33A) 121.7(10) C(48A)-C(47A)-C(33A) 119.4(11) C(47A)-C(48A)-C(49A) 119.1(11) C(50A)-C(49A)-C(48A) 118.4(11) C(51A)-C(50A)-C(49A) 121.9(12) C(50A)-C(51A)-C(52A) 120.2(12) C(51A)-C(52A)-C(47A) 121.4(11) N(1B)-C(1B)-C(2B) 176.4(13) N(2B)-C(3B)-C(4B) 126.9(11) C(9B)-C(4B)-C(5B) 120.0(11) C(9B)-C(4B)-C(3B) 125.3(11) C(5B)-C(4B)-C(3B) 114.7(10) C(6B)-C(5B)-C(4B) 120.8(11) C(5B)-C(6B)-C(7B) 119.1(11) C(6B)-C(7B)-C(8B) 123.5(11) C(9B)-C(8B)-C(7B) 116.6(10) C(9B)-C(8B)-C(22B) 124.1(10) C(7B)-C(8B)-C(22B) 119.4(10) O(1B)-C(9B)-C(4B) 121.6(10) O(1B)-C(9B)-C(8B) 118.4(10) C(4B)-C(9B)-C(8B) 120.0(10) C(11B)-C(10B)-C(15B) 122.8(10) C(11B)-C(10B)-N(2B) 118.1(10) C(15B)-C(10B)-N(2B) 119.1(9) C(10B)-C(11B)-C(12B) 117.4(11) C(10B)-C(11B)-C(19B) 123.7(10) C(12B)-C(11B)-C(19B) 118.8(10) C(13B)-C(12B)-C(11B) 119.4(11) C(14B)-C(13B)-C(12B) 120.7(11) C(15B)-C(14B)-C(13B) 121.2(12) C(14B)-C(15B)-C(10B) 118.2(10) C(14B)-C(15B)-C(16B) 119.2(11) C(10B)-C(15B)-C(16B) 122.3(10) C(15B)-C(16B)-C(17B) 114.2(10) C(15B)-C(16B)-C(18B) 110.5(8) C(17B)-C(16B)-C(18B) 109.1(10) C(21B)-C(19B)-C(11B) 114.5(10) C(21B)-C(19B)-C(20B) 107.1(9) C(11B)-C(19B)-C(20B) 109.9(9) C(23B)-C(22B)-C(27B) 118.3(11) C(23B)-C(22B)-C(8B) 122.3(11) C(27B)-C(22B)-C(8B) 119.3(10)
238
C(22B)-C(23B)-C(24B) 122.3(12) C(25B)-C(24B)-C(23B) 117.5(11) C(26B)-C(25B)-C(24B) 121.2(11) C(25B)-C(26B)-C(27B) 121.3(12) C(26B)-C(27B)-C(22B) 119.2(11) N(3B)-C(28B)-C(29B) 129.8(11) C(28B)-C(29B)-C(30B) 116.7(11) C(28B)-C(29B)-C(34B) 122.8(11) C(30B)-C(29B)-C(34B) 120.4(10) C(31B)-C(30B)-C(29B) 120.9(11) C(30B)-C(31B)-C(32B) 118.2(11) C(33B)-C(32B)-C(31B) 123.6(11) C(32B)-C(33B)-C(34B) 119.5(10) C(32B)-C(33B)-C(47B) 119.9(10) C(34B)-C(33B)-C(47B) 120.5(10) O(2B)-C(34B)-C(33B) 121.8(10) O(2B)-C(34B)-C(29B) 120.5(11) C(33B)-C(34B)-C(29B) 117.3(10) C(40B)-C(35B)-N(3B) 121.3(9) C(40B)-C(35B)-C(36B) 118.3(10) N(3B)-C(35B)-C(36B) 120.3(10) C(37B)-C(36B)-C(35B) 120.7(10) C(37B)-C(36B)-C(44B) 120.3(10) C(35B)-C(36B)-C(44B) 119.0(9) C(38B)-C(37B)-C(36B) 120.0(11) C(37B)-C(38B)-C(39B) 121.9(10) C(38B)-C(39B)-C(40B) 118.8(10) C(35B)-C(40B)-C(39B) 120.2(10) C(35B)-C(40B)-C(41B) 121.9(10) C(39B)-C(40B)-C(41B) 117.7(10) C(40B)-C(41B)-C(43B) 111.2(9) C(40B)-C(41B)-C(42B) 112.1(10) C(43B)-C(41B)-C(42B) 107.9(9) C(46B)-C(44B)-C(45B) 110.7(9)
C(46B)-C(44B)-C(36B) 108.9(9) C(45B)-C(44B)-C(36B) 112.4(9) C(52B)-C(47B)-C(48B) 118.1(11) C(52B)-C(47B)-C(33B) 122.4(10) C(48B)-C(47B)-C(33B) 119.2(11) C(49B)-C(48B)-C(47B) 120.1(11) C(48B)-C(49B)-C(50B) 121.6(11) C(49B)-C(50B)-C(51B) 120.6(11) C(52B)-C(51B)-C(50B) 115.9(11) C(51B)-C(52B)-C(47B) 123.7(11) C(6S)-C(1S)-C(7S) 160(3) C(6S)-C(1S)-C(2S) 95.0(12) C(7S)-C(1S)-C(2S) 100.1(16) C(3S)-C(2S)-C(1S) 124.4(15) C(4S)-C(3S)-C(2S) 114.3(18) C(3S)-C(4S)-C(5S) 120.2(14) C(6S)-C(5S)-C(4S) 127.6(18) C(1S)-C(6S)-C(5S) 138.0(16) C(13S)-C(8S)-C(9S) 121.6(15) C(13S)-C(8S)-C(14S) 118.3(14) C(9S)-C(8S)-C(14S) 119.5(13) C(8S)-C(9S)-C(10S) 117.6(15) C(11S)-C(10S)-C(9S) 119.3(16) C(12S)-C(11S)-C(10S) 119.5(16) C(13S)-C(12S)-C(11S) 122.0(16) C(8S)-C(13S)-C(12S) 119.4(16) C(20S)-C(15S)-C(21S) 124.7(15) C(20S)-C(15S)-C(16S) 119.0(10) C(21S)-C(15S)-C(16S) 116.2(15) C(17S)-C(16S)-C(15S) 116.4(12) C(18S)-C(17S)-C(16S) 127.6(13) C(17S)-C(18S)-C(19S) 115.5(11) C(20S)-C(19S)-C(18S) 118.8(11) C(19S)-C(20S)-C(15S) 122.5(12)
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239
Table C.9. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 8. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Cr(1) 5747(1) 5598(1) 1016(1) 19(1) Cl(1) 5747(2) 5655(2) -348(2) 102(1) O(1) 6581(2) 4677(2) 611(2) 24(1) O(2) 4958(2) 6562(2) 1498(2) 22(1) N(1) 5566(3) 5185(2) 2302(2) 24(1) N(2) 7308(3) 6967(2) 1498(2) 25(1) C(1) 6353(3) 3760(3) 746(2) 27(1) C(2) 6692(4) 2997(3) 51(3) 33(1) C(3) 6540(5) 2041(3) 149(3) 41(1) C(4) 6038(5) 1750(3) 948(3) 50(1) C(5) 5883(7) 741(4) 1039(3) 67(2) C(6) 5393(8) 445(4) 1798(4) 79(2) C(7) 5035(7) 1146(4) 2487(3) 71(2) C(8) 5155(6) 2124(4) 2418(3) 57(2) C(9) 5681(5) 2473(3) 1654(3) 43(1) C(10) 5847(4) 3499(3) 1546(3) 32(1) C(11) 5551(4) 4256(3) 2288(3) 31(1) C(12) 5209(3) 5751(3) 3180(2) 27(1) C(13) 4020(4) 5530(3) 3212(3) 30(1) C(14) 3704(4) 6127(3) 4044(3) 35(1) C(15) 4541(4) 6903(3) 4814(3) 37(1) C(16) 5702(4) 7071(3) 4789(3) 37(1) C(17) 6065(4) 6498(3) 3978(3) 33(1) C(18) 3045(4) 4630(3) 2421(3) 33(1) C(19) 2301(5) 3777(4) 2850(3) 54(1) C(20) 2284(4) 5031(4) 1946(3) 47(1) C(21) 7343(4) 6638(4) 3998(3) 42(1) C(22) 8183(5) 7732(6) 4702(5) 79(2) C(23) 7536(6) 5737(6) 4269(4) 66(2) C(24) 5316(3) 7486(3) 2212(2) 22(1) C(25) 4440(3) 7872(3) 2576(2) 27(1) C(26) 4736(4) 8844(3) 3290(3) 29(1) C(27) 5917(4) 9515(3) 3713(3) 30(1) C(28) 6201(4) 10528(3) 4440(3) 41(1) C(29) 7335(5) 11182(4) 4850(4) 64(2) C(30) 8220(5) 10842(5) 4533(5) 87(3) C(31) 7965(4) 9855(4) 3814(4) 66(2)
240
C(32) 6814(4) 9164(3) 3381(3) 34(1) C(33) 6499(3) 8129(3) 2613(3) 27(1) C(34) 7406(3) 7866(3) 2163(3) 31(1) C(35) 8298(3) 7091(3) 955(3) 33(1) C(36) 8441(3) 7706(3) 331(3) 37(1) C(37) 9390(4) 7815(4) -195(3) 53(1) C(38) 10165(4) 7350(6) -91(4) 67(2) C(39) 10024(4) 6782(5) 544(4) 63(2) C(40) 9098(4) 6631(4) 1086(3) 42(1) C(41) 7669(4) 8307(3) 250(3) 42(1) C(42) 7271(5) 8181(4) -801(4) 50(1) C(43) 8307(6) 9520(4) 838(5) 68(2) C(44) 9038(4) 6101(4) 1857(3) 46(1) C(45) 9907(5) 6911(4) 2776(4) 54(1) C(46) 9292(5) 5079(5) 1504(5) 73(2) C(49A) 1898(13) 7240(18) 6907(11) 46(2) Cl(2A) 1146(9) 6286(6) 5757(6) 46(2) Cl(3A) 1097(7) 7793(6) 7679(5) 46(2) C(49B) 1699(18) 7470(20) 6720(20) 99(4) Cl(2B) 1116(12) 6368(9) 5569(10) 99(4) Cl(3B) 681(10) 7904(6) 7270(10) 99(4) C(49C) 1870(19) 7290(50) 6780(30) 88(4) Cl(2C) 846(13) 6177(11) 5826(9) 88(4) Cl(3C) 856(12) 7456(16) 7538(9) 88(4) C(50A) 1539(10) 9833(9) 2332(8) 50(1) Cl(4A) 2055(2) 9762(2) 3445(2) 50(1) Cl(5A) 780(2) 10699(2) 2575(2) 50(1) C(50B) 1210(80) 9350(60) 1970(50) 26(4) Cl(4B) 2426(13) 8883(12) 2106(14) 26(4) Cl(5B) 1002(10) 10066(12) 3202(13) 26(4) C(50C) 1260(40) 9370(30) 1990(30) 59(2) Cl(4C) 2465(6) 9141(9) 2214(6) 59(2) Cl(5C) 1088(5) 10360(9) 2966(6) 59(2) _______________________________________________________________________ Table C.10. Bond lengths [Å] and angles [°] for 8. _______________________________________________________________________ Cr(1)-O(1) 1.921(2) Cr(1)-O(2) 1.938(2) Cr(1)-Cl(1)#1 1.999(3) Cr(1)-Cl(1) 2.002(2) Cr(1)-N(2) 2.089(3) Cr(1)-N(1) 2.106(3)
Cl(1)-Cr(1)#1 1.999(3) O(1)-C(1) 1.300(4) O(2)-C(24) 1.312(4) N(1)-C(11) 1.305(5) N(1)-C(12) 1.459(4) N(2)-C(34) 1.307(4)
241
N(2)-C(35) 1.458(4) C(1)-C(10) 1.411(5) C(1)-C(2) 1.435(5) C(2)-C(3) 1.351(5) C(3)-C(4) 1.423(7) C(4)-C(5) 1.419(6) C(4)-C(9) 1.420(6) C(5)-C(6) 1.368(9) C(6)-C(7) 1.389(8) C(7)-C(8) 1.374(6) C(8)-C(9) 1.420(7) C(9)-C(10) 1.450(5) C(10)-C(11) 1.433(5) C(12)-C(13) 1.397(6) C(12)-C(17) 1.403(5) C(13)-C(14) 1.404(5) C(13)-C(18) 1.526(5) C(14)-C(15) 1.380(6) C(15)-C(16) 1.376(7) C(16)-C(17) 1.401(5) C(17)-C(21) 1.523(7) C(18)-C(20) 1.516(7) C(18)-C(19) 1.535(6) C(21)-C(22) 1.531(7) C(21)-C(23) 1.539(7) C(24)-C(33) 1.410(5) C(24)-C(25) 1.432(5) C(25)-C(26) 1.363(5) C(26)-C(27) 1.420(6) C(27)-C(28) 1.413(5) C(27)-C(32) 1.417(6) C(28)-C(29) 1.367(7) C(29)-C(30) 1.389(8) C(30)-C(31) 1.387(6) C(31)-C(32) 1.399(6) C(32)-C(33) 1.455(5) C(33)-C(34) 1.425(5) C(35)-C(36) 1.405(6) C(35)-C(40) 1.413(6) C(36)-C(37) 1.402(6) C(36)-C(41) 1.524(7) C(37)-C(38) 1.381(9) C(38)-C(39) 1.370(10) C(39)-C(40) 1.393(7)
C(40)-C(44) 1.512(8) C(41)-C(42) 1.528(7) C(41)-C(43) 1.547(6) C(44)-C(46) 1.536(6) C(44)-C(45) 1.537(6) C(49A)-Cl(3A) 1.717(13) C(49A)-Cl(2A) 1.767(12) C(49B)-Cl(3B) 1.717(15) C(49B)-Cl(2B) 1.807(15) C(49C)-Cl(3C) 1.720(16) C(49C)-Cl(2C) 1.776(16) C(50A)-Cl(5A) 1.769(11) C(50A)-Cl(4A) 1.768(11) C(50B)-Cl(5B) 1.84(8) C(50B)-Cl(4B) 1.89(10) C(50C)-Cl(5C) 1.74(4) C(50C)-Cl(4C) 1.69(5) O(1)-Cr(1)-O(2) 176.73(10) O(1)-Cr(1)-Cl(1)#1 89.21(11) O(2)-Cr(1)-Cl(1)#1 93.12(11) O(1)-Cr(1)-Cl(1) 85.52(10) O(2)-Cr(1)-Cl(1) 97.15(10) Cl(1)#1-Cr(1)-Cl(1) 79.74(11) O(1)-Cr(1)-N(2) 91.67(12) O(2)-Cr(1)-N(2) 86.41(11) Cl(1)#1-Cr(1)-N(2) 170.45(11) Cl(1)-Cr(1)-N(2) 90.85(11) O(1)-Cr(1)-N(1) 87.96(11) O(2)-Cr(1)-N(1) 89.74(11) Cl(1)#1-Cr(1)-N(1) 89.97(11) Cl(1)-Cr(1)-N(1) 167.87(11) N(2)-Cr(1)-N(1) 99.56(12) Cr(1)#1-Cl(1)-Cr(1) 100.26(11) C(1)-O(1)-Cr(1) 126.6(2) C(24)-O(2)-Cr(1) 130.2(2) C(11)-N(1)-C(12) 114.1(3) C(11)-N(1)-Cr(1) 119.7(2) C(12)-N(1)-Cr(1) 125.0(2) C(34)-N(2)-C(35) 112.9(3) C(34)-N(2)-Cr(1) 123.6(2) C(35)-N(2)-Cr(1) 121.9(2) O(1)-C(1)-C(10) 124.1(3) O(1)-C(1)-C(2) 116.8(3)
242
C(10)-C(1)-C(2) 119.0(3) C(3)-C(2)-C(1) 121.4(4) C(2)-C(3)-C(4) 121.3(4) C(5)-C(4)-C(9) 119.9(5) C(5)-C(4)-C(3) 120.5(4) C(9)-C(4)-C(3) 119.6(4) C(6)-C(5)-C(4) 121.2(5) C(5)-C(6)-C(7) 119.1(4) C(8)-C(7)-C(6) 121.4(5) C(7)-C(8)-C(9) 121.3(5) C(4)-C(9)-C(8) 116.9(4) C(4)-C(9)-C(10) 119.0(4) C(8)-C(9)-C(10) 124.1(4) C(1)-C(10)-C(11) 121.2(3) C(1)-C(10)-C(9) 119.8(3) C(11)-C(10)-C(9) 119.0(4) N(1)-C(11)-C(10) 128.6(3) C(13)-C(12)-C(17) 121.5(3) C(13)-C(12)-N(1) 119.3(3) C(17)-C(12)-N(1) 119.3(3) C(12)-C(13)-C(14) 118.1(4) C(12)-C(13)-C(18) 123.5(3) C(14)-C(13)-C(18) 118.3(4) C(15)-C(14)-C(13) 121.1(4) C(16)-C(15)-C(14) 119.8(4) C(15)-C(16)-C(17) 121.4(4) C(16)-C(17)-C(12) 118.0(4) C(16)-C(17)-C(21) 120.3(4) C(12)-C(17)-C(21) 121.6(3) C(20)-C(18)-C(13) 113.1(3) C(20)-C(18)-C(19) 110.9(4) C(13)-C(18)-C(19) 109.8(3) C(17)-C(21)-C(22) 112.7(4) C(17)-C(21)-C(23) 111.1(4) C(22)-C(21)-C(23) 109.3(5) O(2)-C(24)-C(33) 124.2(3) O(2)-C(24)-C(25) 117.1(3) C(33)-C(24)-C(25) 118.7(3) C(26)-C(25)-C(24) 121.1(4)
C(25)-C(26)-C(27) 121.9(3) C(28)-C(27)-C(32) 120.3(4) C(28)-C(27)-C(26) 120.7(4) C(32)-C(27)-C(26) 119.0(3) C(29)-C(28)-C(27) 121.2(4) C(28)-C(29)-C(30) 118.9(4) C(31)-C(30)-C(29) 121.0(5) C(30)-C(31)-C(32) 121.6(5) C(31)-C(32)-C(27) 117.0(4) C(31)-C(32)-C(33) 123.9(4) C(27)-C(32)-C(33) 119.1(4) C(24)-C(33)-C(34) 120.2(3) C(24)-C(33)-C(32) 120.2(3) C(34)-C(33)-C(32) 118.7(3) N(2)-C(34)-C(33) 127.8(3) C(36)-C(35)-C(40) 122.0(4) C(36)-C(35)-N(2) 117.8(4) C(40)-C(35)-N(2) 120.2(4) C(37)-C(36)-C(35) 117.5(5) C(37)-C(36)-C(41) 119.1(4) C(35)-C(36)-C(41) 123.3(3) C(38)-C(37)-C(36) 121.2(5) C(39)-C(38)-C(37) 120.0(4) C(38)-C(39)-C(40) 122.1(5) C(39)-C(40)-C(35) 117.1(5) C(39)-C(40)-C(44) 120.6(5) C(35)-C(40)-C(44) 121.9(4) C(36)-C(41)-C(42) 114.0(4) C(36)-C(41)-C(43) 110.5(4) C(42)-C(41)-C(43) 108.8(4) C(40)-C(44)-C(46) 113.0(5) C(40)-C(44)-C(45) 109.2(4) C(46)-C(44)-C(45) 109.8(4) Cl(3A)-C(49A)-Cl(2A) 117.1(10) Cl(3B)-C(49B)-Cl(2B) 114.6(13) Cl(3C)-C(49C)-Cl(2C) 95.6(12) Cl(5A)-C(50A)-Cl(4A) 109.6(6) Cl(5B)-C(50B)-Cl(4B) 108(4) Cl(5C)-C(50C)-Cl(4C) 113.1(19)
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APPENDIX D
BOND DISTANCES AND ANGLES CORRESPONDING TO SOLID STATE
STRUCTURES IN CHAPTER V*
Table D.1. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Fe(1) 4144(1) 1414(1) 4005(1) 31(1) N(1) 3740(6) 398(6) 4470(5) 37(1) N(2) 3437(6) 688(6) 3080(5) 37(1) O(1) 4932(4) 1683(5) 4978(4) 36(1) O(2) 5020(4) 1511(5) 3589(4) 39(1) O(3) 3265(5) 2246(5) 3734(4) 42(1) C(1) 3218(7) -230(7) 3957(6) 37(1) C(2) 3923(7) 317(8) 5174(6) 37(1) C(3) 4417(7) 878(8) 5743(6) 37(1) C(4) 4889(7) 1559(8) 5631(6) 37(1) C(5) 5353(7) 2100(7) 6218(6) 38(1) C(6) 5282(7) 1939(7) 6901(6) 38(1) C(7) 4811(7) 1281(8) 7033(6) 38(1) C(8) 4396(7) 731(8) 6462(6) 38(1) C(9) 4713(7) 1210(7) 7782(6) 39(1) C(10) 4308(7) 2020(7) 7926(6) 40(1) C(11) 4121(7) 481(7) 7817(6) 40(1) C(12) 5645(7) 1097(7) 8389(6) 39(1) C(13) 5868(7) 2851(7) 6120(6) 38(1) C(14) 6296(7) 3344(7) 6824(6) 38(1) C(15) 6634(7) 2570(7) 5878(6) 38(1) C(16) 5244(7) 3437(7) 5525(6) 39(1) C(17) 2759(7) 150(7) 3195(6) 37(1) C(18) 3548(7) 710(7) 2482(6) 38(1) _______________ * Appear in the order in which they are described in the chapter.
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C(19) 4227(7) 1171(7) 2329(6) 38(1) C(20) 4974(7) 1530(8) 2902(6) 39(1) C(21) 5653(7) 1926(8) 2718(6) 40(1) C(22) 5524(7) 1951(7) 1987(6) 40(1) C(23) 4784(7) 1627(8) 1390(6) 40(1) C(24) 4150(7) 1225(7) 1588(6) 39(1) C(25) 4745(7) 1700(8) 603(6) 42(1) C(26) 4655(8) 2643(7) 380(6) 43(1) C(27) 3923(7) 1265(7) 56(6) 42(1) C(28) 5576(7) 1352(8) 534(6) 44(1) C(29) 6475(7) 2272(8) 3336(6) 41(1) C(30) 6212(7) 2973(7) 3751(6) 41(1) C(31) 6962(7) 1597(7) 3865(6) 41(1) C(32) 7126(7) 2658(7) 3014(6) 41(1) C(33) 3123(7) 2952(8) 4037(6) 43(1) C(34) 3382(7) 3723(8) 3832(6) 43(1) C(35) 3248(7) 4420(8) 4201(6) 44(1) C(36) 2890(7) 4371(8) 4737(6) 44(1) C(37) 2625(7) 3643(8) 4908(6) 44(1) C(38) 2717(7) 2905(8) 4564(6) 44(1) C(39) 2366(7) 2134(8) 4741(7) 46(1) C(40) 1798(7) 1630(8) 4172(7) 47(1) C(41) 1384(8) 931(8) 4323(7) 48(1) C(42) 1580(7) 713(8) 5059(7) 48(1) C(43) 2119(7) 1207(8) 5619(7) 48(1) C(44) 2514(7) 1895(8) 5472(7) 47(1) C(45) 3770(7) 3806(8) 3263(6) 43(1) C(46) 3531(7) 3298(8) 2642(6) 43(1) C(47) 3872(7) 3441(8) 2102(6) 43(1) C(48) 4441(7) 4081(8) 2144(6) 43(1) C(49) 4677(7) 4590(8) 2763(6) 43(1) C(50) 4378(7) 4452(8) 3327(7) 43(1) C(1S) 2144(11) 9389(10) 7851(9) 78(2) Cl(1') 1709(6) 8871(5) 8135(5) 78(2) Cl(2') 1382(17) 9814(15) 6830(13) 108(4) Cl(1S) 2253(5) 10096(5) 8449(5) 78(2) Cl(2S) 1350(20) 9435(17) 6962(15) 108(4) _______________________________________________________________________
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Table D.2. Bond lengths [Å] and angles [°] for 1. _______________________________________________________________________ Fe(1)-O(3) 1.876(8) Fe(1)-O(2) 1.887(6) Fe(1)-O(1) 1.894(7) Fe(1)-N(2) 2.091(9) Fe(1)-N(1) 2.094(9) N(1)-C(2) 1.301(12) N(1)-C(1) 1.448(13) N(2)-C(18) 1.249(12) N(2)-C(17) 1.478(13) O(1)-C(4) 1.321(11) O(2)-C(20) 1.316(12) O(3)-C(33) 1.343(13) C(1)-C(17) 1.518(14) C(2)-C(3) 1.420(15) C(3)-C(4) 1.399(15) C(3)-C(8) 1.439(14) C(4)-C(5) 1.409(15) C(5)-C(6) 1.407(14) C(5)-C(13) 1.520(15) C(6)-C(7) 1.386(15) C(7)-C(8) 1.384(14) C(7)-C(9) 1.536(14) C(9)-C(10) 1.535(15) C(9)-C(11) 1.532(15) C(9)-C(12) 1.531(14) C(13)-C(14) 1.511(14) C(13)-C(15) 1.549(13) C(13)-C(16) 1.540(14) C(18)-C(19) 1.447(14) C(19)-C(24) 1.409(14) C(19)-C(20) 1.419(15) C(20)-C(21) 1.429(14) C(21)-C(22) 1.364(14) C(21)-C(29) 1.520(15) C(22)-C(23) 1.416(15) C(23)-C(24) 1.384(14) C(23)-C(25) 1.520(15) C(25)-C(28) 1.505(14) C(25)-C(27) 1.521(15) C(25)-C(26) 1.572(15) C(29)-C(31) 1.501(15) C(29)-C(32) 1.546(14)
C(29)-C(30) 1.542(14) C(33)-C(38) 1.418(15) C(33)-C(34) 1.418(16) C(34)-C(35) 1.397(15) C(34)-C(45) 1.475(15) C(35)-C(36) 1.377(14) C(36)-C(37) 1.335(15) C(37)-C(38) 1.402(15) C(38)-C(39) 1.460(16) C(39)-C(40) 1.400(15) C(39)-C(44) 1.411(15) C(40)-C(41) 1.398(15) C(41)-C(42) 1.396(15) C(42)-C(43) 1.367(16) C(43)-C(44) 1.363(15) C(45)-C(46) 1.391(15) C(45)-C(50) 1.402(15) C(46)-C(47) 1.381(14) C(47)-C(48) 1.364(15) C(48)-C(49) 1.392(15) C(49)-C(50) 1.379(14) C(1S)-Cl(1') 1.340(15) C(1S)-Cl(1S) 1.594(16) C(1S)-Cl(2S) 1.73(3) C(1S)-Cl(2') 2.02(3) Cl(1')-Cl(1S) 2.154(12) Cl(1')-Cl(2S) 2.33(2) Cl(2')-Cl(2S) 0.67(2) O(3)-Fe(1)-O(2) 115.4(3) O(3)-Fe(1)-O(1) 105.5(3) O(2)-Fe(1)-O(1) 95.0(3) O(3)-Fe(1)-N(2) 92.9(3) O(2)-Fe(1)-N(2) 85.7(3) O(1)-Fe(1)-N(2) 159.1(3) O(3)-Fe(1)-N(1) 110.9(3) O(2)-Fe(1)-N(1) 131.3(3) O(1)-Fe(1)-N(1) 86.8(3) N(2)-Fe(1)-N(1) 77.3(4) C(2)-N(1)-C(1) 120.1(10) C(2)-N(1)-Fe(1) 123.7(8) C(1)-N(1)-Fe(1) 116.2(7)
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C(18)-N(2)-C(17) 122.4(10) C(18)-N(2)-Fe(1) 124.7(8) C(17)-N(2)-Fe(1) 112.9(6) C(4)-O(1)-Fe(1) 132.5(7) C(20)-O(2)-Fe(1) 132.8(7) C(33)-O(3)-Fe(1) 135.9(7) N(1)-C(1)-C(17) 109.6(9) N(1)-C(2)-C(3) 126.8(12) C(4)-C(3)-C(8) 119.9(11) C(4)-C(3)-C(2) 123.7(10) C(8)-C(3)-C(2) 116.4(11) O(1)-C(4)-C(3) 120.1(10) O(1)-C(4)-C(5) 119.1(11) C(3)-C(4)-C(5) 120.7(10) C(6)-C(5)-C(4) 116.7(11) C(6)-C(5)-C(13) 120.7(10) C(4)-C(5)-C(13) 122.5(10) C(7)-C(6)-C(5) 124.5(11) C(8)-C(7)-C(6) 118.1(10) C(8)-C(7)-C(9) 121.9(11) C(6)-C(7)-C(9) 119.8(10) C(7)-C(8)-C(3) 120.0(11) C(10)-C(9)-C(11) 109.2(9) C(10)-C(9)-C(7) 108.4(9) C(11)-C(9)-C(7) 113.0(10) C(10)-C(9)-C(12) 108.7(9) C(11)-C(9)-C(12) 108.7(9) C(7)-C(9)-C(12) 108.8(9) C(14)-C(13)-C(5) 112.7(9) C(14)-C(13)-C(15) 106.9(9) C(5)-C(13)-C(15) 110.1(9) C(14)-C(13)-C(16) 107.9(9) C(5)-C(13)-C(16) 110.6(9) C(15)-C(13)-C(16) 108.4(9) N(2)-C(17)-C(1) 105.8(8) N(2)-C(18)-C(19) 126.6(11) C(24)-C(19)-C(20) 120.3(10) C(24)-C(19)-C(18) 117.8(10) C(20)-C(19)-C(18) 121.9(10) O(2)-C(20)-C(21) 121.0(10) O(2)-C(20)-C(19) 120.0(10) C(21)-C(20)-C(19) 119.0(10) C(22)-C(21)-C(20) 116.8(10) C(22)-C(21)-C(29) 124.2(10)
C(20)-C(21)-C(29) 119.0(10) C(21)-C(22)-C(23) 126.8(11) C(24)-C(23)-C(22) 115.0(10) C(24)-C(23)-C(25) 124.7(10) C(22)-C(23)-C(25) 120.3(10) C(23)-C(24)-C(19) 122.1(11) C(28)-C(25)-C(23) 111.4(9) C(28)-C(25)-C(27) 109.5(9) C(23)-C(25)-C(27) 111.4(9) C(28)-C(25)-C(26) 109.1(9) C(23)-C(25)-C(26) 108.6(10) C(27)-C(25)-C(26) 106.7(9) C(31)-C(29)-C(21) 110.7(10) C(31)-C(29)-C(32) 108.3(9) C(21)-C(29)-C(32) 110.2(9) C(31)-C(29)-C(30) 110.2(9) C(21)-C(29)-C(30) 110.8(9) C(32)-C(29)-C(30) 106.5(10) O(3)-C(33)-C(38) 118.7(11) O(3)-C(33)-C(34) 120.0(10) C(38)-C(33)-C(34) 121.4(12) C(35)-C(34)-C(33) 116.0(10) C(35)-C(34)-C(45) 120.7(12) C(33)-C(34)-C(45) 123.2(11) C(36)-C(35)-C(34) 122.6(12) C(37)-C(36)-C(35) 120.6(12) C(36)-C(37)-C(38) 121.6(11) C(33)-C(38)-C(37) 117.8(12) C(33)-C(38)-C(39) 123.0(12) C(37)-C(38)-C(39) 119.2(10) C(40)-C(39)-C(44) 117.0(12) C(40)-C(39)-C(38) 120.1(11) C(44)-C(39)-C(38) 122.7(12) C(39)-C(40)-C(41) 121.4(12) C(42)-C(41)-C(40) 118.8(12) C(43)-C(42)-C(41) 120.3(13) C(42)-C(43)-C(44) 120.8(12) C(43)-C(44)-C(39) 121.6(12) C(46)-C(45)-C(50) 117.9(11) C(46)-C(45)-C(34) 123.3(11) C(50)-C(45)-C(34) 118.8(11) C(45)-C(46)-C(47) 120.7(12) C(48)-C(47)-C(46) 122.3(12) C(47)-C(48)-C(49) 117.0(11)
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C(50)-C(49)-C(48) 122.5(12) C(49)-C(50)-C(45) 119.6(12) Cl(1')-C(1S)-Cl(1S) 94.1(10) Cl(1')-C(1S)-Cl(2S) 97.9(14) Cl(1S)-C(1S)-Cl(2S) 122.7(13) Cl(1')-C(1S)-Cl(2') 113.7(13) Cl(1S)-C(1S)-Cl(2') 109.7(11) Cl(2S)-C(1S)-Cl(2') 18.6(12)
C(1S)-Cl(1')-Cl(1S) 47.6(7) C(1S)-Cl(1')-Cl(2S) 47.3(11) Cl(1S)-Cl(1')-Cl(2S) 81.1(9) Cl(2S)-Cl(2')-C(1S) 55(4) C(1S)-Cl(1S)-Cl(1') 38.4(6) Cl(2')-Cl(2S)-C(1S) 107(6) Cl(2')-Cl(2S)-Cl(1') 135(5) C(1S)-Cl(2S)-Cl(1') 34.8(7)
_______________________________________________________________________ Table D.3. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 2. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Fe(1) 5424(1) 6147(1) 8639(1) 27(1) N(1) 5817(2) 6130(3) 7963(1) 25(1) N(2) 5200(2) 4401(4) 8333(1) 29(1) O(1) 5619(1) 7873(3) 8649(1) 30(1) O(2) 4661(1) 6482(3) 8570(1) 26(1) O(3) 6135(1) 5270(3) 8825(1) 36(1) O(4) 5283(1) 6110(3) 9336(1) 30(1) C(1) 5765(2) 4966(4) 7687(2) 30(1) C(2) 6146(2) 6977(5) 7813(2) 30(1) C(3) 6248(2) 8188(4) 8028(2) 27(1) C(4) 5975(2) 8597(4) 8436(2) 26(1) C(5) 6079(2) 9848(5) 8610(2) 29(1) C(6) 6442(2) 10570(5) 8372(2) 29(1) C(7) 6725(2) 10175(5) 7961(2) 30(1) C(8) 6617(2) 8987(4) 7800(2) 27(1) C(9) 7112(2) 11079(4) 7722(2) 31(1) C(10) 7396(2) 10466(5) 7298(2) 39(1) C(11) 6786(2) 12227(5) 7536(2) 43(2) C(12) 7544(2) 11512(6) 8073(2) 52(2) C(13) 5770(2) 10345(4) 9041(2) 34(1) C(14) 5169(2) 10438(5) 8908(2) 44(2) C(15) 5839(2) 9486(5) 9474(2) 41(1) C(16) 5959(3) 11650(5) 9181(2) 49(2) C(17) 5614(2) 3895(4) 8020(2) 33(1) C(18) 4736(2) 3868(4) 8368(2) 27(1) C(19) 4281(2) 4429(4) 8611(2) 26(1)
248
C(20) 4263(2) 5732(5) 8703(2) 27(1) C(21) 3796(2) 6221(4) 8931(2) 26(1) C(22) 3399(2) 5387(5) 9056(2) 32(1) C(23) 3408(2) 4078(5) 8969(2) 32(1) C(24) 3851(2) 3646(5) 8732(2) 31(1) C(25) 2943(2) 3194(5) 9119(2) 36(1) C(26) 3166(3) 2163(6) 9436(2) 64(2) C(27) 2684(3) 2653(6) 8687(2) 62(2) C(28) 2506(2) 3899(6) 9396(3) 66(2) C(29) 3756(2) 7630(5) 9048(2) 31(1) C(30) 3218(2) 7968(5) 9283(2) 46(2) C(31) 3800(2) 8441(5) 8600(2) 40(1) C(32) 4201(2) 7995(5) 9399(2) 38(1) C(33) 5391(2) 6333(5) 10157(2) 40(1) C(34) 5596(2) 5933(5) 9690(2) 34(1) C(35) 6112(2) 5400(5) 9650(2) 38(1) C(36) 6347(2) 5078(5) 9228(2) 34(1) C(37) 6892(2) 4469(5) 9219(2) 45(2) N(1S) 5000 -1167(7) 7500 79(3) C(1S) 5000 88(10) 7500 94(5) C(2S) 4790(13) 1144(11) 7541(15) 290(30) _______________________________________________________________________ Table D.4. Bond lengths [Å] and angles [°] for 2. _______________________________________________________________________ Fe(1)-O(1) 1.898(3) Fe(1)-O(2) 1.934(3) Fe(1)-O(4) 2.006(3) Fe(1)-O(3) 2.060(3) Fe(1)-N(2) 2.124(4) Fe(1)-N(1) 2.154(4) N(1)-C(2) 1.288(6) N(1)-C(1) 1.471(6) N(2)-C(18) 1.287(6) N(2)-C(17) 1.461(6) O(1)-C(4) 1.320(5) O(2)-C(20) 1.325(5) O(3)-C(36) 1.273(6) O(4)-C(34) 1.282(6) C(1)-C(17) 1.527(7) C(2)-C(3) 1.446(7) C(3)-C(8) 1.409(6) C(3)-C(4) 1.411(7)
C(4)-C(5) 1.442(7) C(5)-C(6) 1.363(6) C(5)-C(13) 1.539(7) C(6)-C(7) 1.426(7) C(7)-C(8) 1.369(7) C(7)-C(9) 1.522(7) C(9)-C(12) 1.529(8) C(9)-C(10) 1.539(7) C(9)-C(11) 1.555(7) C(13)-C(16) 1.518(7) C(13)-C(15) 1.537(7) C(13)-C(14) 1.538(7) C(18)-C(19) 1.453(6) C(19)-C(24) 1.395(7) C(19)-C(20) 1.411(7) C(20)-C(21) 1.429(6) C(21)-C(22) 1.374(6) C(21)-C(29) 1.538(7)
249
C(22)-C(23) 1.415(7) C(23)-C(24) 1.370(7) C(23)-C(25) 1.549(7) C(25)-C(27) 1.494(8) C(25)-C(26) 1.520(8) C(25)-C(28) 1.537(8) C(29)-C(30) 1.536(7) C(29)-C(32) 1.532(7) C(29)-C(31) 1.540(7) C(33)-C(34) 1.482(7) C(34)-C(35) 1.404(7) C(35)-C(36) 1.377(7) C(36)-C(37) 1.498(7) N(1S)-C(1S) 1.335(12) C(1S)-C(2S)#1 1.243(19) C(1S)-C(2S) 1.243(19) C(2S)-C(2S)#1 1.07(8) O(1)-Fe(1)-O(2) 94.12(13) O(1)-Fe(1)-O(4) 92.92(13) O(2)-Fe(1)-O(4) 85.88(13) O(1)-Fe(1)-O(3) 102.53(14) O(2)-Fe(1)-O(3) 160.81(13) O(4)-Fe(1)-O(3) 83.84(14) O(1)-Fe(1)-N(2) 156.61(15) O(2)-Fe(1)-N(2) 82.30(14) O(4)-Fe(1)-N(2) 109.78(14) O(3)-Fe(1)-N(2) 85.99(15) O(1)-Fe(1)-N(1) 84.52(14) O(2)-Fe(1)-N(1) 111.00(14) O(4)-Fe(1)-N(1) 163.04(14) O(3)-Fe(1)-N(1) 80.38(14) N(2)-Fe(1)-N(1) 75.38(15) C(2)-N(1)-C(1) 117.9(4) C(2)-N(1)-Fe(1) 125.3(3) C(1)-N(1)-Fe(1) 116.2(3) C(18)-N(2)-C(17) 121.1(4) C(18)-N(2)-Fe(1) 125.8(3) C(17)-N(2)-Fe(1) 112.7(3) C(4)-O(1)-Fe(1) 136.8(3) C(20)-O(2)-Fe(1) 126.1(3) C(36)-O(3)-Fe(1) 130.7(3) C(34)-O(4)-Fe(1) 131.8(3) N(1)-C(1)-C(17) 108.6(4)
N(1)-C(2)-C(3) 126.4(4) C(8)-C(3)-C(4) 120.3(4) C(8)-C(3)-C(2) 117.2(4) C(4)-C(3)-C(2) 122.4(4) O(1)-C(4)-C(3) 121.2(4) O(1)-C(4)-C(5) 120.1(4) C(3)-C(4)-C(5) 118.7(4) C(6)-C(5)-C(4) 117.9(4) C(6)-C(5)-C(13) 122.1(4) C(4)-C(5)-C(13) 120.0(4) C(5)-C(6)-C(7) 124.5(5) C(8)-C(7)-C(6) 116.7(4) C(8)-C(7)-C(9) 123.8(4) C(6)-C(7)-C(9) 119.5(4) C(7)-C(8)-C(3) 122.0(5) C(7)-C(9)-C(12) 110.0(4) C(7)-C(9)-C(10) 111.8(4) C(12)-C(9)-C(10) 108.3(4) C(7)-C(9)-C(11) 108.6(4) C(12)-C(9)-C(11) 110.2(4) C(10)-C(9)-C(11) 107.9(4) C(16)-C(13)-C(5) 111.5(4) C(16)-C(13)-C(15) 107.6(5) C(5)-C(13)-C(15) 112.0(4) C(16)-C(13)-C(14) 107.6(4) C(5)-C(13)-C(14) 108.2(4) C(15)-C(13)-C(14) 109.8(4) N(2)-C(17)-C(1) 106.0(4) N(2)-C(18)-C(19) 123.6(4) C(24)-C(19)-C(20) 121.1(5) C(24)-C(19)-C(18) 117.8(4) C(20)-C(19)-C(18) 121.0(4) O(2)-C(20)-C(19) 121.1(4) O(2)-C(20)-C(21) 121.0(4) C(19)-C(20)-C(21) 117.8(4) C(22)-C(21)-C(20) 117.8(4) C(22)-C(21)-C(29) 121.8(4) C(20)-C(21)-C(29) 120.4(4) C(21)-C(22)-C(23) 125.3(5) C(24)-C(23)-C(22) 115.5(5) C(24)-C(23)-C(25) 122.1(5) C(22)-C(23)-C(25) 122.4(5) C(23)-C(24)-C(19) 122.4(5) C(27)-C(25)-C(26) 111.1(5)
250
C(27)-C(25)-C(28) 107.9(5) C(26)-C(25)-C(28) 107.7(5) C(27)-C(25)-C(23) 109.1(4) C(26)-C(25)-C(23) 109.3(4) C(28)-C(25)-C(23) 111.8(4) C(30)-C(29)-C(32) 106.5(4) C(30)-C(29)-C(21) 112.2(4) C(32)-C(29)-C(21) 109.9(4) C(30)-C(29)-C(31) 106.9(4) C(32)-C(29)-C(31) 109.9(4) C(21)-C(29)-C(31) 111.2(4)
O(4)-C(34)-C(35) 123.0(5) O(4)-C(34)-C(33) 116.7(5) C(35)-C(34)-C(33) 120.4(5) C(36)-C(35)-C(34) 124.2(5) O(3)-C(36)-C(35) 124.3(5) O(3)-C(36)-C(37) 115.1(5) C(35)-C(36)-C(37) 120.6(5) C(2S)#1-C(1S)-C(2S) 51(3) C(2S)#1-C(1S)-N(1S) 154.6(17) C(2S)-C(1S)-N(1S) 154.6(17) C(2S)#1-C(2S)-C(1S) 64.6(17)
_______________________________________________________________________ Table D.5. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 3. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Fe(1) 153(1) 4947(1) 1566(1) 18(1) N(1) -176(1) 3778(1) 1231(1) 20(1) N(2) -576(1) 5132(1) 485(2) 20(1) O(1) 896(1) 4453(1) 1786(1) 23(1) O(2) 391(1) 6008(1) 1382(1) 23(1) O(3) 0 5025(2) 2500 23(1) C(1) -792(1) 3760(2) 741(2) 25(1) C(2) 99(1) 3142(2) 1532(2) 22(1) C(3) 697(1) 3109(2) 2084(2) 21(1) C(4) 1074(1) 3780(2) 2204(2) 22(1) C(5) 1646(1) 3703(2) 2775(2) 25(1) C(6) 1809(1) 2979(2) 3189(2) 26(1) C(7) 1446(1) 2313(2) 3087(2) 24(1) C(8) 893(1) 2400(2) 2524(2) 23(1) C(9) 1636(1) 1551(2) 3612(2) 27(1) C(10) 1403(2) 1580(2) 4332(2) 38(1) C(11) 1403(2) 801(2) 3086(2) 44(1) C(12) 2298(2) 1472(2) 3979(2) 39(1) C(13) 2061(1) 4418(2) 2948(2) 33(1) C(14) 1813(2) 5119(2) 3299(3) 46(1) C(15) 2159(2) 4675(3) 2151(3) 50(1) C(16) 2651(2) 4213(2) 3599(3) 51(1) C(17) -915(1) 4423(2) 93(2) 23(1)
251
C(18) -744(1) 5815(2) 145(2) 23(1) C(19) -459(1) 6574(2) 399(2) 23(1) C(20) 96(1) 6643(2) 1022(2) 22(1) C(21) 333(1) 7425(2) 1246(2) 25(1) C(22) 13(2) 8065(2) 810(2) 30(1) C(23) -533(2) 8008(2) 176(2) 30(1) C(24) -757(1) 7254(2) -15(2) 28(1) C(25) -845(2) 8761(2) -254(2) 41(1) C(26) -1438(2) 8572(2) -895(2) 46(1) C(27) -924(2) 9334(3) 401(3) 62(1) C(28) -478(2) 9178(2) -697(2) 45(1) C(29) 915(1) 7539(2) 1956(2) 30(1) C(30) 878(2) 7193(2) 2768(2) 33(1) C(31) 1404(1) 7130(2) 1745(2) 33(1) C(32) 1073(2) 8425(2) 2115(2) 40(1) C(1S) 2500 2500 0 142(6) C(2S) 2399(10) 3954(10) 304(15) 347(15) O(1S) 2523(3) 3240(6) 564(3) 122(3) O(2S) 2313(5) 3084(7) -2(10) 221(5) _______________________________________________________________________ Table D.6. Bond lengths [Å] and angles [°] for 3. _______________________________________________________________________ Fe(1)-O(3) 1.7653(10) Fe(1)-O(1) 1.917(2) Fe(1)-O(2) 1.926(2) Fe(1)-N(2) 2.100(3) Fe(1)-N(1) 2.116(3) N(1)-C(2) 1.267(4) N(1)-C(1) 1.453(4) N(2)-C(18) 1.282(4) N(2)-C(17) 1.469(4) O(1)-C(4) 1.322(4) O(2)-C(20) 1.311(4) O(3)-Fe(1)#1 1.7653(10) C(1)-C(17) 1.519(4) C(2)-C(3) 1.444(4) C(3)-C(8) 1.397(4) C(3)-C(4) 1.421(4) C(4)-C(5) 1.411(4) C(5)-C(6) 1.388(4) C(5)-C(13) 1.531(4) C(6)-C(7) 1.397(4)
C(7)-C(8) 1.372(4) C(7)-C(9) 1.534(4) C(9)-C(10) 1.526(5) C(9)-C(11) 1.532(5) C(9)-C(12) 1.530(5) C(13)-C(16) 1.527(5) C(13)-C(14) 1.535(5) C(13)-C(15) 1.524(5) C(18)-C(19) 1.440(4) C(19)-C(20) 1.412(4) C(19)-C(24) 1.403(4) C(20)-C(21) 1.428(4) C(21)-C(22) 1.382(5) C(21)-C(29) 1.531(5) C(22)-C(23) 1.404(5) C(23)-C(24) 1.368(5) C(23)-C(25) 1.522(5) C(25)-C(26) 1.521(6) C(25)-C(28) 1.530(5) C(25)-C(27) 1.534(5)
252
C(29)-C(32) 1.531(5) C(29)-C(30) 1.534(5) C(29)-C(31) 1.529(5) C(1S)-O(2S) 1.078(12) C(1S)-O(2S)#2 1.078(12) C(1S)-O(1S) 1.556(8) C(1S)-O(1S)#2 1.556(8) C(2S)-O(1S) 1.27(2) C(2S)-O(2S) 1.534(17) O(1S)-O(2S) 0.960(17) O(3)-Fe(1)-O(1) 109.92(7) O(3)-Fe(1)-O(2) 104.60(10) O(1)-Fe(1)-O(2) 96.10(9) O(3)-Fe(1)-N(2) 113.58(8) O(1)-Fe(1)-N(2) 134.26(9) O(2)-Fe(1)-N(2) 86.30(9) O(3)-Fe(1)-N(1) 97.50(10) O(1)-Fe(1)-N(1) 84.44(9) O(2)-Fe(1)-N(1) 156.18(9) N(2)-Fe(1)-N(1) 76.67(9) C(2)-N(1)-C(1) 121.2(3) C(2)-N(1)-Fe(1) 124.4(2) C(1)-N(1)-Fe(1) 113.42(18) C(18)-N(2)-C(17) 117.9(2) C(18)-N(2)-Fe(1) 124.9(2) C(17)-N(2)-Fe(1) 117.20(18) C(4)-O(1)-Fe(1) 125.83(17) C(20)-O(2)-Fe(1) 132.15(19) Fe(1)-O(3)-Fe(1)#1 171.63(17) N(1)-C(1)-C(17) 108.0(2) N(1)-C(2)-C(3) 125.0(3) C(8)-C(3)-C(4) 120.4(3) C(8)-C(3)-C(2) 117.8(3) C(4)-C(3)-C(2) 121.8(3) O(1)-C(4)-C(5) 120.9(3) O(1)-C(4)-C(3) 121.1(3) C(5)-C(4)-C(3) 118.0(3) C(6)-C(5)-C(4) 118.2(3) C(6)-C(5)-C(13) 121.8(3) C(4)-C(5)-C(13) 119.9(3) C(5)-C(6)-C(7) 124.9(3) C(8)-C(7)-C(6) 115.9(3) C(8)-C(7)-C(9) 121.5(3)
C(6)-C(7)-C(9) 122.5(3) C(7)-C(8)-C(3) 122.6(3) C(7)-C(9)-C(10) 108.8(2) C(7)-C(9)-C(11) 111.2(3) C(10)-C(9)-C(11) 109.3(3) C(7)-C(9)-C(12) 112.0(3) C(10)-C(9)-C(12) 108.3(3) C(11)-C(9)-C(12) 107.2(3) C(5)-C(13)-C(16) 111.4(3) C(5)-C(13)-C(14) 110.1(3) C(16)-C(13)-C(14) 107.0(3) C(5)-C(13)-C(15) 110.4(3) C(16)-C(13)-C(15) 108.0(3) C(14)-C(13)-C(15) 109.9(3) N(2)-C(17)-C(1) 108.6(2) N(2)-C(18)-C(19) 126.9(3) C(20)-C(19)-C(24) 120.8(3) C(20)-C(19)-C(18) 122.7(3) C(24)-C(19)-C(18) 116.6(3) O(2)-C(20)-C(19) 121.2(3) O(2)-C(20)-C(21) 120.5(3) C(19)-C(20)-C(21) 118.3(3) C(22)-C(21)-C(20) 117.5(3) C(22)-C(21)-C(29) 122.0(3) C(20)-C(21)-C(29) 120.5(3) C(21)-C(22)-C(23) 125.1(3) C(24)-C(23)-C(22) 116.3(3) C(24)-C(23)-C(25) 123.6(3) C(22)-C(23)-C(25) 120.1(3) C(23)-C(24)-C(19) 122.0(3) C(23)-C(25)-C(26) 111.7(3) C(23)-C(25)-C(28) 109.3(3) C(26)-C(25)-C(28) 108.6(3) C(23)-C(25)-C(27) 109.5(3) C(26)-C(25)-C(27) 108.8(3) C(28)-C(25)-C(27) 108.8(3) C(21)-C(29)-C(32) 111.7(3) C(21)-C(29)-C(30) 109.7(3) C(32)-C(29)-C(30) 107.2(3) C(21)-C(29)-C(31) 110.5(3) C(32)-C(29)-C(31) 107.7(3) C(30)-C(29)-C(31) 110.0(3) O(2S)-C(1S)-O(2S)#2 180.0(13) O(2S)-C(1S)-O(1S) 37.5(10)
253
O(2S)#2-C(1S)-O(1S) 142.5(10) O(2S)-C(1S)-O(1S)#2 142.5(10) O(2S)#2-C(1S)-O(1S)#2 37.5(10) O(1S)-C(1S)-O(1S)#2 180.0(4) O(1S)-C(2S)-O(2S) 38.6(8) O(2S)-O(1S)-C(2S) 85.6(15)
O(2S)-O(1S)-C(1S) 43.1(9) C(2S)-O(1S)-C(1S) 125.1(11) O(1S)-O(2S)-C(1S) 99.4(16) O(1S)-O(2S)-C(2S) 55.8(14) C(1S)-O(2S)-C(2S) 148.0(16)
_______________________________________________________________________
254
APPENDIX E
BOND DISTANCES AND ANGLES CORRESPONDING TO SOLID STATE
STRUCTURES IN CHAPTER VI*
Table E.1. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 5. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pt(1) 6820(1) 3754(1) 8669(1) 35(1) P(1) 8145(3) 3752(6) 8294(2) 40(1) P(2) 5620(3) 3758(5) 7956(2) 33(1) P(3) 6706(5) 2396(5) 9193(3) 32(2) P(4) 6755(5) 5125(5) 9195(3) 30(2) N(1) 9270(14) 4692(17) 7629(9) 64(4) N(2) 10069(11) 3692(17) 8374(7) 54(3) N(3) 9218(14) 2881(17) 7542(8) 61(4) N(4) 3669(10) 3769(15) 7607(6) 41(3) N(5) 4615(12) 2854(14) 7010(7) 45(3) N(6) 4588(12) 4680(14) 7017(7) 44(3) N(7) 5732(11) 1260(20) 9859(6) 40(3) N(8) 7437(11) 1190(20) 10091(6) 39(3) N(9) 6628(15) 376(15) 9251(9) 37(4) N(10) 6729(15) 7179(16) 9289(10) 38(4) N(11) 7547(10) 6260(20) 10122(6) 38(3) N(12) 5826(10) 6250(20) 9881(6) 34(3) C(1) 8435(17) 4810(20) 7874(11) 64(5) C(2) 9328(12) 3650(20) 8708(8) 50(5) C(3) 8327(16) 2786(19) 7796(10) 59(5) C(4) 9249(16) 3880(20) 7265(9) 67(4) C(5) 10122(16) 4580(20) 8055(10) 60(4) C(6) 10050(16) 2860(20) 8029(10) 58(4) _______________ * Appear in the order in which they are described in the chapter.
255
C(7) 4420(12) 3779(19) 8126(7) 40(4) C(8) 5461(16) 2735(17) 7449(9) 46(5) C(9) 5424(16) 4787(18) 7439(9) 48(5) C(10) 3738(15) 2841(17) 7248(9) 43(4) C(11) 4671(13) 3767(19) 6694(8) 44(4) C(12) 3762(14) 4633(17) 7234(9) 40(4) C(13) 5700(17) 2172(18) 9560(11) 42(5) C(14) 7624(16) 2132(18) 9807(10) 37(5) C(15) 6701(13) 1210(20) 8861(7) 33(4) C(16) 6515(12) 1230(20) 10296(8) 42(4) C(17) 7412(16) 311(19) 9703(10) 39(4) C(18) 5769(17) 400(20) 9498(11) 42(4) C(19) 6788(13) 6363(19) 8890(8) 35(4) C(20) 7673(15) 5331(18) 9799(9) 34(5) C(21) 5746(15) 5277(18) 9560(10) 30(4) C(22) 7515(17) 7160(20) 9718(11) 42(4) C(23) 6605(12) 6250(20) 10331(7) 39(3) C(24) 5883(16) 7080(19) 9526(11) 38(4) C(25) 9311(19) 2100(20) 7146(11) 87(7) C(26) 2692(15) 3770(20) 7790(9) 69(6) C(27) 8236(15) 1027(19) 10572(10) 60(7) C(28) 8350(15) 6360(20) 10601(9) 64(6) S(1) 3242(4) 6388(7) 8704(2) 48(2) F(1) 2400(10) 5707(11) 8492(6) 104(6) O(1) 3401(8) 6269(16) 9295(4) 49(4) O(2) 2928(11) 7355(9) 8521(6) 59(5) O(3) 3986(9) 6009(11) 8438(6) 57(5) S(2) 9194(7) 296(8) 8656(4) 110(3) O(5) 10248(11) 310(20) 8654(10) 230(20) O(4) 9205(14) 1215(13) 8976(7) 95(7) O(6) 8778(16) 295(19) 8055(9) 146(10) S(3) 3102(5) 1102(6) 8673(2) 48(2) F(3) 2164(10) 1608(11) 8402(6) 107(6) O(7) 3152(10) 1283(17) 9250(4) 65(4) O(8) 3800(9) 1607(13) 8440(7) 80(7) O(9) 2983(11) 98(9) 8509(6) 60(5) S(4) 9859(5) 3522(7) 594(3) 79(3) F(4) 9760(30) 4660(20) 235(15) 1600(200) O(10) 9907(14) 2936(18) 150(9) 132(10) O(11) 10668(8) 3737(16) 950(6) 62(5) O(12) 9090(16) 3560(40) 818(11) 350(40) F(2) 8980(20) -531(15) 8923(10) 300(20) O(1W) 1397(13) 2207(19) 1664(8) 117(8) ______________________________________________________________________
256
Table E.2. Bond lengths [Å] and angles [°] for 5. _______________________________________________________________________ Pt(1)-P(2) 2.261(5) Pt(1)-P(1) 2.266(5) Pt(1)-P(3) 2.270(7) Pt(1)-P(4) 2.275(7) P(1)-C(3) 1.84(2) P(1)-C(1) 1.85(3) P(1)-C(2) 1.86(2) P(2)-C(8) 1.85(2) P(2)-C(7) 1.862(17) P(2)-C(9) 1.87(2) P(3)-C(15) 1.81(3) P(3)-C(13) 1.86(2) P(3)-C(14) 1.88(2) P(4)-C(20) 1.85(2) P(4)-C(21) 1.85(2) P(4)-C(19) 1.85(3) N(1)-C(4) 1.42(3) N(1)-C(1) 1.45(3) N(1)-C(5) 1.49(3) N(2)-C(6) 1.40(3) N(2)-C(5) 1.45(3) N(2)-C(2) 1.45(2) N(3)-C(25) 1.46(3) N(3)-C(4) 1.52(3) N(3)-C(3) 1.53(3) N(3)-C(6) 1.56(3) N(4)-C(12) 1.51(3) N(4)-C(7) 1.54(2) N(4)-C(10) 1.55(3) N(4)-C(26) 1.56(2) N(5)-C(11) 1.47(3) N(5)-C(10) 1.49(3) N(5)-C(8) 1.51(3) N(6)-C(12) 1.39(2) N(6)-C(9) 1.47(3) N(6)-C(11) 1.49(3) N(7)-C(13) 1.43(3) N(7)-C(16) 1.43(2) N(7)-C(18) 1.48(3) N(8)-C(14) 1.50(3) N(8)-C(16) 1.51(2) N(8)-C(17) 1.53(3)
N(8)-C(27) 1.53(2) N(9)-C(17) 1.46(3) N(9)-C(18) 1.47(3) N(9)-C(15) 1.49(3) N(10)-C(22) 1.42(3) N(10)-C(24) 1.45(3) N(10)-C(19) 1.49(3) N(11)-C(20) 1.52(3) N(11)-C(28) 1.52(2) N(11)-C(23) 1.54(2) N(11)-C(22) 1.56(3) N(12)-C(24) 1.44(3) N(12)-C(23) 1.45(2) N(12)-C(21) 1.53(3) S(1)-O(1) 1.427(11) S(1)-O(3) 1.444(11) S(1)-O(2) 1.445(12) S(1)-F(1) 1.563(15) S(2)-F(2) 1.36(2) S(2)-O(4) 1.475(15) S(2)-O(6) 1.489(16) S(2)-O(5) 1.541(16) S(3)-O(7) 1.413(11) S(3)-O(8) 1.420(13) S(3)-O(9) 1.430(12) S(3)-F(3) 1.582(15) S(4)-O(12) 1.323(15) S(4)-O(10) 1.353(13) S(4)-O(11) 1.381(12) S(4)-F(4) 1.77(3) F(4)-F(4)#1 1.72(9) P(2)-Pt(1)-P(1) 107.46(19) P(2)-Pt(1)-P(3) 108.3(3) P(1)-Pt(1)-P(3) 111.5(3) P(2)-Pt(1)-P(4) 109.4(2) P(1)-Pt(1)-P(4) 109.9(3) P(3)-Pt(1)-P(4) 110.16(19) C(3)-P(1)-C(1) 97.4(10) C(3)-P(1)-C(2) 94.9(11) C(1)-P(1)-C(2) 94.7(11) C(3)-P(1)-Pt(1) 119.1(8)
257
C(1)-P(1)-Pt(1) 120.2(8) C(2)-P(1)-Pt(1) 124.1(6) C(8)-P(2)-C(7) 97.8(11) C(8)-P(2)-C(9) 97.5(9) C(7)-P(2)-C(9) 95.0(10) C(8)-P(2)-Pt(1) 120.5(7) C(7)-P(2)-Pt(1) 118.2(6) C(9)-P(2)-Pt(1) 122.2(8) C(15)-P(3)-C(13) 96.8(10) C(15)-P(3)-C(14) 97.7(10) C(13)-P(3)-C(14) 96.1(12) C(15)-P(3)-Pt(1) 118.6(7) C(13)-P(3)-Pt(1) 122.4(9) C(14)-P(3)-Pt(1) 119.7(8) C(20)-P(4)-C(21) 97.7(11) C(20)-P(4)-C(19) 96.8(11) C(21)-P(4)-C(19) 99.3(10) C(20)-P(4)-Pt(1) 118.8(8) C(21)-P(4)-Pt(1) 118.0(9) C(19)-P(4)-Pt(1) 121.4(7) C(4)-N(1)-C(1) 114(2) C(4)-N(1)-C(5) 107(2) C(1)-N(1)-C(5) 112.9(19) C(6)-N(2)-C(5) 110.8(17) C(6)-N(2)-C(2) 111(2) C(5)-N(2)-C(2) 116(2) C(25)-N(3)-C(4) 110.6(19) C(25)-N(3)-C(3) 112(2) C(4)-N(3)-C(3) 109.9(19) C(25)-N(3)-C(6) 110(2) C(4)-N(3)-C(6) 106.0(19) C(3)-N(3)-C(6) 107.7(17) C(12)-N(4)-C(7) 111.5(17) C(12)-N(4)-C(10) 106.5(14) C(7)-N(4)-C(10) 111.6(16) C(12)-N(4)-C(26) 109.8(17) C(7)-N(4)-C(26) 109.5(13) C(10)-N(4)-C(26) 107.9(18) C(11)-N(5)-C(10) 109.5(17) C(11)-N(5)-C(8) 110.7(17) C(10)-N(5)-C(8) 112.6(16) C(12)-N(6)-C(9) 114.5(17) C(12)-N(6)-C(11) 108.0(18) C(9)-N(6)-C(11) 108.8(17)
C(13)-N(7)-C(16) 111(2) C(13)-N(7)-C(18) 113.2(15) C(16)-N(7)-C(18) 108(2) C(14)-N(8)-C(16) 111(2) C(14)-N(8)-C(17) 112.3(14) C(16)-N(8)-C(17) 107(2) C(14)-N(8)-C(27) 107.8(18) C(16)-N(8)-C(27) 111.4(14) C(17)-N(8)-C(27) 107.2(19) C(17)-N(9)-C(18) 108(2) C(17)-N(9)-C(15) 113.4(19) C(18)-N(9)-C(15) 113.2(18) C(22)-N(10)-C(24) 110(2) C(22)-N(10)-C(19) 109.7(19) C(24)-N(10)-C(19) 109.2(19) C(20)-N(11)-C(28) 109.0(18) C(20)-N(11)-C(23) 110(2) C(28)-N(11)-C(23) 111.7(13) C(20)-N(11)-C(22) 109.0(13) C(28)-N(11)-C(22) 111(2) C(23)-N(11)-C(22) 106.2(19) C(24)-N(12)-C(23) 110(2) C(24)-N(12)-C(21) 112.7(14) C(23)-N(12)-C(21) 112(2) N(1)-C(1)-P(1) 114.7(18) N(2)-C(2)-P(1) 113.9(13) N(3)-C(3)-P(1) 115.1(16) N(1)-C(4)-N(3) 115.1(18) N(2)-C(5)-N(1) 110.1(19) N(2)-C(6)-N(3) 112(2) N(4)-C(7)-P(2) 113.1(11) N(5)-C(8)-P(2) 113.1(15) N(6)-C(9)-P(2) 114.5(16) N(5)-C(10)-N(4) 110.2(17) N(5)-C(11)-N(6) 114.7(14) N(6)-C(12)-N(4) 115.3(17) N(7)-C(13)-P(3) 114.8(16) N(8)-C(14)-P(3) 111.7(15) N(9)-C(15)-P(3) 113.2(13) N(7)-C(16)-N(8) 114.0(14) N(9)-C(17)-N(8) 110.8(18) N(9)-C(18)-N(7) 112(2) N(10)-C(19)-P(4) 114.6(14) N(11)-C(20)-P(4) 113.9(14)
258
N(12)-C(21)-P(4) 109.8(14) N(10)-C(22)-N(11) 115(2) N(12)-C(23)-N(11) 112.8(13) N(12)-C(24)-N(10) 116.5(19) O(1)-S(1)-O(3) 113.2(10) O(1)-S(1)-O(2) 114.0(12) O(3)-S(1)-O(2) 114.5(10) O(1)-S(1)-F(1) 105.0(9) O(3)-S(1)-F(1) 104.3(8) O(2)-S(1)-F(1) 104.4(8) F(2)-S(2)-O(4) 116.0(11) F(2)-S(2)-O(6) 112.1(12) O(4)-S(2)-O(6) 119.1(15) F(2)-S(2)-O(5) 108.4(12) O(4)-S(2)-O(5) 93.7(15)
O(6)-S(2)-O(5) 104.6(15) O(7)-S(3)-O(8) 112.4(11) O(7)-S(3)-O(9) 115.4(13) O(8)-S(3)-O(9) 114.7(11) O(7)-S(3)-F(3) 104.0(9) O(8)-S(3)-F(3) 104.5(8) O(9)-S(3)-F(3) 104.1(8) O(12)-S(4)-O(10) 120.1(16) O(12)-S(4)-O(11) 115.7(13) O(10)-S(4)-O(11) 118.5(12) O(12)-S(4)-F(4) 99.1(14) O(10)-S(4)-F(4) 97.9(12) O(11)-S(4)-F(4) 96.8(12) F(4)#1-F(4)-S(4) 142(4)
_______________________________________________________________________ Table E.3. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 7. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pt(1) 1861(1) 7687(1) 3284(1) 8(1) P(1) 1889(2) 8629(2) 2041(2) 10(1) P(2) 3143(2) 6687(2) 3246(2) 11(1) P(3) 2179(2) 8871(2) 4692(2) 10(1) P(4) 248(2) 6573(2) 3172(2) 9(1) N(1) 1951(9) 8768(9) 69(7) 15(2) N(2) 1106(10) 10074(9) 1005(8) 19(2) N(3) 3084(9) 10290(9) 1253(8) 19(2) N(4) 4237(9) 5412(11) 2061(9) 23(2) N(5) 5278(9) 6530(10) 3551(9) 21(2) N(6) 3959(9) 4930(9) 3668(9) 18(2) N(7) 1631(9) 10606(8) 5839(8) 16(2) N(8) 2162(8) 9222(8) 6733(7) 12(2) N(9) 3508(9) 10453(9) 6088(8) 17(2) N(10) -1137(9) 5057(10) 3905(9) 21(2) N(11) -1143(9) 4712(9) 2131(8) 17(2) N(12) -1983(8) 6142(8) 2900(8) 13(2) C(1) 1863(10) 7999(9) 751(8) 12(2) C(2) 2949(10) 9522(10) 274(9) 15(2)
259
C(3) 3107(10) 9687(10) 2091(9) 16(2) C(4) 901(11) 9469(10) 1811(10) 17(2) C(5) 1066(11) 9350(11) 82(9) 18(2) C(6) 2096(13) 10841(10) 1224(10) 22(3) C(7) 3066(10) 5484(10) 3837(10) 16(2) C(8) 4574(10) 7305(11) 3710(11) 19(3) C(9) 3345(12) 6054(12) 2034(10) 22(3) C(10) 5289(11) 6136(13) 2523(10) 23(3) C(11) 5003(11) 5629(11) 4074(10) 21(3) C(12) 3952(12) 4512(11) 2656(11) 22(3) C(13) 1943(10) 8342(9) 5836(8) 13(2) C(14) 1377(10) 9933(10) 4872(9) 15(2) C(15) 3513(10) 9755(11) 5146(9) 16(2) C(16) 1406(10) 10018(10) 6616(9) 13(2) C(17) 3325(11) 9843(11) 6853(9) 19(3) C(18) 2763(11) 11160(10) 6013(9) 17(2) C(19) -61(10) 5437(11) 2151(10) 18(2) C(20) -88(11) 5776(12) 4150(10) 21(3) C(21) -1036(10) 7020(10) 2994(10) 15(2) C(22) -1198(11) 4242(10) 3078(12) 25(3) C(23) -2033(10) 5355(11) 2037(10) 17(2) C(24) -2003(10) 5641(11) 3769(10) 19(3) C(25) 4364(17) 4965(18) 1043(12) 43(5) C(26) 4063(13) 11117(13) 1352(12) 31(3) C(27) 1976(12) 8728(11) 7627(9) 20(3) C(28) -1321(13) 3822(13) 1267(14) 37(4) I(1) 4019(3) 7044(4) 6758(4) 155(2) I(2) 5129(3) 8183(4) 995(3) 149(1) I(3) 8675(1) 6543(1) 9737(1) 27(1) I(4) 8866(1) 7474(1) 6458(1) 21(1) O(1S) 2354(9) 1490(8) 8801(8) 26(2) O(2S) 3756(10) 1880(9) 3862(9) 33(3) O(3S) 3963(11) 6772(11) 9004(11) 44(3) _______________________________________________________________________ Table E.4. Bond lengths [Å] and angles [°] for 7. _______________________________________________________________________ Pt(1)-P(3) 2.253(3) Pt(1)-P(1) 2.260(3) Pt(1)-P(2) 2.262(3) Pt(1)-P(4) 2.264(3) P(1)-C(4) 1.839(13) P(1)-C(1) 1.859(12)
P(1)-C(3) 1.859(12) P(2)-C(9) 1.835(13) P(2)-C(7) 1.848(13) P(2)-C(8) 1.865(13) P(3)-C(14) 1.857(12) P(3)-C(13) 1.862(12)
260
P(3)-C(15) 1.860(13) P(4)-C(19) 1.838(13) P(4)-C(21) 1.843(13) P(4)-C(20) 1.867(14) N(1)-C(2) 1.429(17) N(1)-C(5) 1.468(17) N(1)-C(1) 1.470(15) N(2)-C(6) 1.429(19) N(2)-C(5) 1.465(17) N(2)-C(4) 1.481(16) N(3)-C(26) 1.468(18) N(3)-C(3) 1.499(16) N(3)-C(2) 1.538(16) N(3)-C(6) 1.558(19) N(4)-C(25) 1.491(19) N(4)-C(10) 1.509(19) N(4)-C(9) 1.527(17) N(4)-C(12) 1.536(19) N(5)-C(10) 1.455(19) N(5)-C(11) 1.468(18) N(5)-C(8) 1.468(17) N(6)-C(12) 1.437(18) N(6)-C(11) 1.472(17) N(6)-C(7) 1.475(16) N(7)-C(16) 1.438(16) N(7)-C(14) 1.462(16) N(7)-C(18) 1.472(17) N(8)-C(27) 1.506(16) N(8)-C(13) 1.522(14) N(8)-C(17) 1.535(16) N(8)-C(16) 1.546(15) N(9)-C(17) 1.432(17) N(9)-C(18) 1.438(17) N(9)-C(15) 1.481(16) N(10)-C(22) 1.43(2) N(10)-C(24) 1.460(17) N(10)-C(20) 1.461(16) N(11)-C(28) 1.502(17) N(11)-C(19) 1.516(16) N(11)-C(23) 1.531(17) N(11)-C(22) 1.54(2) N(12)-C(23) 1.443(16) N(12)-C(24) 1.458(17) N(12)-C(21) 1.477(16)
P(3)-Pt(1)-P(1) 107.97(11) P(3)-Pt(1)-P(2) 109.49(11) P(1)-Pt(1)-P(2) 110.33(11) P(3)-Pt(1)-P(4) 110.10(10) P(1)-Pt(1)-P(4) 110.43(11) P(2)-Pt(1)-P(4) 108.52(11) C(4)-P(1)-C(1) 97.1(6) C(4)-P(1)-C(3) 96.9(6) C(1)-P(1)-C(3) 96.2(6) C(4)-P(1)-Pt(1) 121.8(4) C(1)-P(1)-Pt(1) 123.0(4) C(3)-P(1)-Pt(1) 116.0(4) C(9)-P(2)-C(7) 97.5(6) C(9)-P(2)-C(8) 97.5(7) C(7)-P(2)-C(8) 97.3(6) C(9)-P(2)-Pt(1) 116.2(4) C(7)-P(2)-Pt(1) 122.1(4) C(8)-P(2)-Pt(1) 121.0(4) C(14)-P(3)-C(13) 96.3(6) C(14)-P(3)-C(15) 96.8(6) C(13)-P(3)-C(15) 97.8(6) C(14)-P(3)-Pt(1) 119.9(4) C(13)-P(3)-Pt(1) 118.0(4) C(15)-P(3)-Pt(1) 122.6(4) C(19)-P(4)-C(21) 97.1(6) C(19)-P(4)-C(20) 96.9(7) C(21)-P(4)-C(20) 96.8(6) C(19)-P(4)-Pt(1) 115.9(4) C(21)-P(4)-Pt(1) 123.2(4) C(20)-P(4)-Pt(1) 121.3(4) C(2)-N(1)-C(5) 109.4(10) C(2)-N(1)-C(1) 112.3(10) C(5)-N(1)-C(1) 110.9(10) C(6)-N(2)-C(5) 110.8(11) C(6)-N(2)-C(4) 112.1(11) C(5)-N(2)-C(4) 111.5(10) C(26)-N(3)-C(3) 110.6(11) C(26)-N(3)-C(2) 110.0(11) C(3)-N(3)-C(2) 111.1(10) C(26)-N(3)-C(6) 109.0(12) C(3)-N(3)-C(6) 109.7(10) C(2)-N(3)-C(6) 106.3(10) C(25)-N(4)-C(10) 107.6(13)
261
C(25)-N(4)-C(9) 109.3(11) C(10)-N(4)-C(9) 110.2(11) C(25)-N(4)-C(12) 111.2(13) C(10)-N(4)-C(12) 109.6(11) C(9)-N(4)-C(12) 108.9(11) C(10)-N(5)-C(11) 110.5(12) C(10)-N(5)-C(8) 112.9(11) C(11)-N(5)-C(8) 111.5(11) C(12)-N(6)-C(11) 110.2(11) C(12)-N(6)-C(7) 112.8(11) C(11)-N(6)-C(7) 111.6(10) C(16)-N(7)-C(14) 113.3(10) C(16)-N(7)-C(18) 109.3(10) C(14)-N(7)-C(18) 110.5(10) C(27)-N(8)-C(13) 109.7(9) C(27)-N(8)-C(17) 109.4(10) C(13)-N(8)-C(17) 110.1(9) C(27)-N(8)-C(16) 109.3(9) C(13)-N(8)-C(16) 109.8(9) C(17)-N(8)-C(16) 108.6(9) C(17)-N(9)-C(18) 111.2(11) C(17)-N(9)-C(15) 111.9(10) C(18)-N(9)-C(15) 112.4(10) C(22)-N(10)-C(24) 110.2(11) C(22)-N(10)-C(20) 113.2(12) C(24)-N(10)-C(20) 112.2(11) C(28)-N(11)-C(19) 108.8(10) C(28)-N(11)-C(23) 109.0(11) C(19)-N(11)-C(23) 109.9(10) C(28)-N(11)-C(22) 110.2(12)
C(19)-N(11)-C(22) 111.0(10) C(23)-N(11)-C(22) 107.9(10) C(23)-N(12)-C(24) 111.1(10) C(23)-N(12)-C(21) 110.9(10) C(24)-N(12)-C(21) 111.7(10) N(1)-C(1)-P(1) 114.0(8) N(1)-C(2)-N(3) 113.6(10) N(3)-C(3)-P(1) 113.9(9) N(2)-C(4)-P(1) 113.1(9) N(2)-C(5)-N(1) 113.5(10) N(2)-C(6)-N(3) 112.1(10) N(6)-C(7)-P(2) 112.3(9) N(5)-C(8)-P(2) 112.0(9) N(4)-C(9)-P(2) 113.5(9) N(5)-C(10)-N(4) 111.7(10) N(6)-C(11)-N(5) 112.7(11) N(6)-C(12)-N(4) 111.9(11) N(8)-C(13)-P(3) 113.0(8) N(7)-C(14)-P(3) 113.9(9) N(9)-C(15)-P(3) 111.8(8) N(7)-C(16)-N(8) 111.8(10) N(9)-C(17)-N(8) 111.9(11) N(9)-C(18)-N(7) 114.0(10) N(11)-C(19)-P(4) 113.1(8) N(10)-C(20)-P(4) 112.5(9) N(12)-C(21)-P(4) 113.5(8) N(10)-C(22)-N(11) 111.8(10) N(12)-C(23)-N(11) 111.8(10) N(10)-C(24)-N(12) 112.7(10)
_______________________________________________________________________ Table E.5. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 8'. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pd(1) 0 1741(1) 10052(1) 16(1) Ni(1) 0 3399(2) 7179(2) 16(1)
262
Cl(1) 1272(14) 60(20) 10740(30) 31(5) C(1) 1230(40) 270(60) 10820(80) 17(15) Cl(2) 3807(2) 2525(3) 1937(4) 33(1) S(1) 1205(2) 3568(3) 9139(4) 20(1) N(1) 1147(5) 2918(9) 5592(11) 16(2) C(9) 2375(7) 2801(11) 8003(16) 20(2) C(2) 2263(8) 3257(10) 6289(17) 25(3) C(3) 1042(8) 3608(12) 3935(15) 22(2) C(4) 0 4498(17) 3740(20) 25(3) C(6) 1049(7) 1304(9) 5448(12) 13(2) C(7) 0 794(14) 4653(18) 19(3) C(8) 5000 2627(15) 3150(20) 23(3) _______________________________________________________________________ Table E.6. Bond lengths [Å] and angles [°] for 8'. _______________________________________________________________________ Pd(1)-C(1)#1 2.12(5) Pd(1)-C(1) 2.12(5) Pd(1)-Cl(1)#1 2.275(19) Pd(1)-Cl(1) 2.275(19) Pd(1)-S(1) 2.368(3) Pd(1)-S(1)#1 2.368(3) Pd(1)-Ni(1) 2.802(2) Ni(1)-N(1)#1 1.960(8) Ni(1)-N(1) 1.960(8) Ni(1)-S(1) 2.179(3) Ni(1)-S(1)#1 2.179(3) Cl(2)-C(8) 1.764(10) S(1)-C(9) 1.847(10) N(1)-C(3) 1.500(15) N(1)-C(6) 1.508(11) N(1)-C(2) 1.512(12) C(9)-C(2) 1.466(18) C(3)-C(4) 1.528(13)
C(4)-C(3)#1 1.528(13) C(6)-C(7) 1.514(12) C(7)-C(6)#1 1.514(12) C(8)-Cl(2)#2 1.764(10) C(1)#1-Pd(1)-C(1) 90(3) C(1)#1-Pd(1)-Cl(1)#1 4(2) C(1)-Pd(1)-Cl(1)#1 88.3(11) C(1)#1-Pd(1)-Cl(1) 88.3(11) C(1)-Pd(1)-Cl(1) 4(2) Cl(1)#1-Pd(1)-Cl(1) 86.3(9) C(1)#1-Pd(1)-S(1) 173.4(15) C(1)-Pd(1)-S(1) 96.4(15) Cl(1)#1-Pd(1)-S(1) 174.5(5) Cl(1)-Pd(1)-S(1) 98.3(5) C(1)#1-Pd(1)-S(1)#1 96.4(15) C(1)-Pd(1)-S(1)#1 173.4(16) Cl(1)#1-Pd(1)-S(1)#1 98.3(5)
263
Cl(1)-Pd(1)-S(1)#1 174.5(5) S(1)-Pd(1)-S(1)#1 77.03(12) C(1)#1-Pd(1)-Ni(1) 126.7(16) C(1)-Pd(1)-Ni(1) 126.7(16) Cl(1)#1-Pd(1)-Ni(1) 125.7(5) Cl(1)-Pd(1)-Ni(1) 125.7(5) S(1)-Pd(1)-Ni(1) 48.99(7) S(1)#1-Pd(1)-Ni(1) 48.99(7) N(1)#1-Ni(1)-N(1) 91.4(5) N(1)#1-Ni(1)-S(1) 169.9(3) N(1)-Ni(1)-S(1) 90.9(2) N(1)#1-Ni(1)-S(1)#1 90.9(2) N(1)-Ni(1)-S(1)#1 169.9(3) S(1)-Ni(1)-S(1)#1 85.14(16) N(1)#1-Ni(1)-Pd(1) 115.2(2) N(1)-Ni(1)-Pd(1) 115.2(2) S(1)-Ni(1)-Pd(1) 55.06(8)
S(1)#1-Ni(1)-Pd(1) 55.06(8) C(9)-S(1)-Ni(1) 97.4(4) C(9)-S(1)-Pd(1) 111.3(3) Ni(1)-S(1)-Pd(1) 75.95(9) C(3)-N(1)-C(6) 110.4(8) C(3)-N(1)-C(2) 109.0(8) C(6)-N(1)-C(2) 107.9(7) C(3)-N(1)-Ni(1) 115.8(6) C(6)-N(1)-Ni(1) 102.8(5) C(2)-N(1)-Ni(1) 110.5(7) C(2)-C(9)-S(1) 107.1(6) C(9)-C(2)-N(1) 112.5(8) N(1)-C(3)-C(4) 113.3(10) C(3)#1-C(4)-C(3) 113.1(13) N(1)-C(6)-C(7) 114.3(8) C(6)-C(7)-C(6)#1 116.0(11) Cl(2)-C(8)-Cl(2)#2 111.6(10)
_______________________________________________________________________ Table E.7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 9. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________________________ x y z U(eq) _______________________________________________________________________ Pd(1) 6269(2) 3615(1) 4965(1) 34(1) Pd(2) 5309(2) 2095(1) 3998(1) 36(1) O(1) 4902(12) 2973(9) 4514(11) 41(5) Ni(1A) 7061(3) 2066(2) 6243(2) 36(1) N(1A) 8434(16) 2262(11) 7138(13) 41(6) N(2A) 7650(20) 1160(13) 6463(14) 56(7) S(1A) 6566(5) 3106(3) 6263(4) 36(2) S(2A) 5528(6) 1680(4) 5350(4) 41(2) C(1) 7549(18) 4259(13) 5385(15) 39(7) C(2) 5590(20) 1239(12) 3523(16) 53(8) C(3) 3937(19) 3126(14) 4516(15) 42(7) C(4) 3062(19) 2678(13) 4114(15) 35(7)
264
C(5) 2040(20) 2857(14) 4068(15) 44(7) C(6) 1850(20) 3446(14) 4491(16) 41(7) C(7) 2730(20) 3825(13) 4895(15) 37(7) C(8) 3728(19) 3717(11) 4910(14) 24(5) C(1A) 7790(20) 3422(12) 7156(14) 38(7) C(2A) 8710(20) 3003(13) 7160(18) 51(8) C(3A) 5850(20) 784(14) 5490(20) 59(9) C(4A) 7010(30) 697(13) 5745(19) 58(9) C(5A) 9260(20) 1871(15) 6985(14) 45(8) C(6A) 8840(20) 1197(12) 6622(18) 48(8) C(7A) 8350(20) 2038(15) 7942(14) 46(8) C(8A) 8300(20) 1295(14) 8024(17) 48(8) C(9A) 7570(20) 936(14) 7291(15) 49(8) Ni(1B) 4515(3) 3556(2) 2747(2) 34(1) N(1B) 3681(18) 4358(11) 2599(13) 45(6) N(2B) 3214(16) 3216(11) 1847(12) 37(6) S(1B) 5925(5) 4052(4) 3616(4) 38(2) S(2B) 5319(5) 2613(4) 2780(4) 42(2) C(1B) 5360(20) 4901(14) 3579(16) 53(8) C(2B) 4190(20) 4821(13) 3297(19) 55(8) C(3B) 4250(20) 2239(14) 1826(17) 53(8) C(4B) 3240(20) 2496(14) 1776(15) 43(7) C(5B) 2600(20) 4165(13) 2579(15) 38(7) C(6B) 2290(20) 3456(15) 2042(16) 54(9) C(7B) 3630(30) 4722(15) 1818(17) 59(9) C(8B) 3030(20) 4316(14) 1084(19) 55(8) C(9B) 3260(20) 3589(15) 1073(16) 51(8) C(1S) 9840(20) 3471(13) 9655(15) 34(7) C(2S) 8730(20) 3511(15) 9447(15) 42(7) C(3S) 8230(20) 2962(19) 9598(15) 59(10) C(4S) 8770(20) 2363(15) 9961(15) 43(7) C(5S) 9860(20) 2346(16) 10141(17) 51(8) C(6S) 10320(20) 2880(15) 9973(13) 34(7) C(7S) 1640(30) 4085(14) 8126(17) 47(8) C(8S) 660(30) 4369(14) 7650(20) 53(8) C(9S) 450(30) 4514(15) 6760(20) 70(11) C(10S) 1260(30) 4429(18) 6450(30) 80(12) C(11S) 2210(30) 4151(16) 6980(20) 62(9) C(12S) 2410(20) 3972(13) 7780(20) 51(8) O(1W) 9438(19) 5229(12) 8955(11) 64(6) O(1S) 10345(17) 4005(10) 9515(15) 69(6) O(2S) 1839(14) 3925(10) 8957(12) 55(5) _______________________________________________________________________
265
Table E.8. Bond lengths [Å] and angles [°] for 9. _______________________________________________________________________ Pd(1)-C(1) 2.02(2) Pd(1)-O(1) 2.104(15) Pd(1)-S(1A) 2.275(7) Pd(1)-S(1B) 2.283(7) Pd(2)-C(2) 1.96(2) Pd(2)-O(1) 2.089(17) Pd(2)-S(2B) 2.271(7) Pd(2)-S(2A) 2.306(7) O(1)-C(3) 1.32(3) Ni(1A)-N(1A) 1.91(2) Ni(1A)-N(2A) 1.93(2) Ni(1A)-S(1A) 2.153(8) Ni(1A)-S(2A) 2.155(8) N(1A)-C(5A) 1.43(3) N(1A)-C(7A) 1.45(3) N(1A)-C(2A) 1.50(3) N(2A)-C(4A) 1.49(4) N(2A)-C(9A) 1.49(3) N(2A)-C(6A) 1.50(3) S(1A)-C(1A) 1.85(2) S(2A)-C(3A) 1.81(3) C(3)-C(4) 1.41(3) C(3)-C(8) 1.41(3) C(4)-C(5) 1.38(3) C(5)-C(6) 1.43(3) C(6)-C(7) 1.33(3) C(7)-C(8) 1.33(3) C(1A)-C(2A) 1.47(3) C(3A)-C(4A) 1.44(4) C(5A)-C(6A) 1.48(3) C(7A)-C(8A) 1.47(3) C(8A)-C(9A) 1.43(3) Ni(1B)-N(1B) 1.89(2) Ni(1B)-N(2B) 1.930(19) Ni(1B)-S(1B) 2.122(7) Ni(1B)-S(2B) 2.130(8) N(1B)-C(2B) 1.43(3) N(1B)-C(7B) 1.46(3) N(1B)-C(5B) 1.48(3) N(2B)-C(4B) 1.42(3) N(2B)-C(6B) 1.46(3) N(2B)-C(9B) 1.51(3)
S(1B)-C(1B) 1.82(3) S(2B)-C(3B) 1.84(3) C(1B)-C(2B) 1.46(4) C(3B)-C(4B) 1.41(3) C(5B)-C(6B) 1.62(3) C(7B)-C(8B) 1.42(4) C(8B)-C(9B) 1.46(3) C(1S)-O(1S) 1.31(3) C(1S)-C(6S) 1.34(3) C(1S)-C(2S) 1.38(3) C(2S)-C(3S) 1.34(4) C(3S)-C(4S) 1.40(4) C(4S)-C(5S) 1.36(4) C(5S)-C(6S) 1.30(3) C(7S)-O(2S) 1.34(3) C(7S)-C(12S) 1.37(3) C(7S)-C(8S) 1.37(4) C(8S)-C(9S) 1.41(4) C(9S)-C(10S) 1.38(4) C(10S)-C(11S) 1.35(4) C(11S)-C(12S) 1.31(4) C(1)-Pd(1)-O(1) 178.1(9) C(1)-Pd(1)-S(1A) 97.2(7) O(1)-Pd(1)-S(1A) 83.8(5) C(1)-Pd(1)-S(1B) 86.2(7) O(1)-Pd(1)-S(1B) 92.8(5) S(1A)-Pd(1)-S(1B) 175.8(3) C(2)-Pd(2)-O(1) 175.6(10) C(2)-Pd(2)-S(2B) 87.7(8) O(1)-Pd(2)-S(2B) 94.9(5) C(2)-Pd(2)-S(2A) 96.7(8) O(1)-Pd(2)-S(2A) 81.3(5) S(2B)-Pd(2)-S(2A) 170.9(3) C(3)-O(1)-Pd(2) 126.4(16) C(3)-O(1)-Pd(1) 124.8(16) Pd(2)-O(1)-Pd(1) 108.7(7) N(1A)-Ni(1A)-N(2A) 80.7(10) N(1A)-Ni(1A)-S(1A) 90.2(7) N(2A)-Ni(1A)-S(1A) 168.9(7) N(1A)-Ni(1A)-S(2A) 170.0(7) N(2A)-Ni(1A)-S(2A) 90.9(8)
266
S(1A)-Ni(1A)-S(2A) 97.5(3) C(5A)-N(1A)-C(7A) 109(2) C(5A)-N(1A)-C(2A) 109(2) C(7A)-N(1A)-C(2A) 112(2) C(5A)-N(1A)-Ni(1A) 108.7(16) C(7A)-N(1A)-Ni(1A) 106.0(15) C(2A)-N(1A)-Ni(1A) 111.5(16) C(4A)-N(2A)-C(9A) 110(2) C(4A)-N(2A)-C(6A) 115(2) C(9A)-N(2A)-C(6A) 107(2) C(4A)-N(2A)-Ni(1A) 110.3(17) C(9A)-N(2A)-Ni(1A) 106.4(17) C(6A)-N(2A)-Ni(1A) 108.2(18) C(1A)-S(1A)-Ni(1A) 98.6(8) C(1A)-S(1A)-Pd(1) 113.5(8) Ni(1A)-S(1A)-Pd(1) 110.4(3) C(3A)-S(2A)-Ni(1A) 97.8(9) C(3A)-S(2A)-Pd(2) 114.3(10) Ni(1A)-S(2A)-Pd(2) 106.7(3) O(1)-C(3)-C(4) 119(2) O(1)-C(3)-C(8) 123(2) C(4)-C(3)-C(8) 118(2) C(5)-C(4)-C(3) 119(2) C(4)-C(5)-C(6) 122(3) C(7)-C(6)-C(5) 115(2) C(8)-C(7)-C(6) 127(2) C(7)-C(8)-C(3) 119(2) C(2A)-C(1A)-S(1A) 107.0(17) C(1A)-C(2A)-N(1A) 111(2) C(4A)-C(3A)-S(2A) 109.2(19) C(3A)-C(4A)-N(2A) 112(2) N(1A)-C(5A)-C(6A) 111(2) C(5A)-C(6A)-N(2A) 109(2) N(1A)-C(7A)-C(8A) 114(2) C(9A)-C(8A)-C(7A) 117(2) C(8A)-C(9A)-N(2A) 112(2) N(1B)-Ni(1B)-N(2B) 83.0(9) N(1B)-Ni(1B)-S(1B) 91.6(7) N(2B)-Ni(1B)-S(1B) 171.7(7) N(1B)-Ni(1B)-S(2B) 173.5(7) N(2B)-Ni(1B)-S(2B) 90.7(7) S(1B)-Ni(1B)-S(2B) 94.5(3) C(2B)-N(1B)-C(7B) 105(2)
C(2B)-N(1B)-C(5B) 110(2) C(7B)-N(1B)-C(5B) 113(2) C(2B)-N(1B)-Ni(1B) 110.6(17) C(7B)-N(1B)-Ni(1B) 110.8(18) C(5B)-N(1B)-Ni(1B) 107.8(16) C(4B)-N(2B)-C(6B) 113(2) C(4B)-N(2B)-C(9B) 114.0(19) C(6B)-N(2B)-C(9B) 110(2) C(4B)-N(2B)-Ni(1B) 111.6(16) C(6B)-N(2B)-Ni(1B) 107.2(15) C(9B)-N(2B)-Ni(1B) 100.3(15) C(1B)-S(1B)-Ni(1B) 98.9(9) C(1B)-S(1B)-Pd(1) 107.9(9) Ni(1B)-S(1B)-Pd(1) 107.2(3) C(3B)-S(2B)-Ni(1B) 96.4(9) C(3B)-S(2B)-Pd(2) 109.3(10) Ni(1B)-S(2B)-Pd(2) 104.0(3) C(2B)-C(1B)-S(1B) 107(2) N(1B)-C(2B)-C(1B) 117(2) C(4B)-C(3B)-S(2B) 108.4(18) C(3B)-C(4B)-N(2B) 114(2) N(1B)-C(5B)-C(6B) 106(2) N(2B)-C(6B)-C(5B) 110(2) C(8B)-C(7B)-N(1B) 108(3) C(7B)-C(8B)-C(9B) 121(3) C(8B)-C(9B)-N(2B) 113(2) O(1S)-C(1S)-C(6S) 125(3) O(1S)-C(1S)-C(2S) 119(3) C(6S)-C(1S)-C(2S) 117(2) C(3S)-C(2S)-C(1S) 118(3) C(2S)-C(3S)-C(4S) 123(3) C(5S)-C(4S)-C(3S) 117(3) C(6S)-C(5S)-C(4S) 119(3) C(5S)-C(6S)-C(1S) 127(3) O(2S)-C(7S)-C(12S) 121(3) O(2S)-C(7S)-C(8S) 118(3) C(12S)-C(7S)-C(8S) 121(3) C(7S)-C(8S)-C(9S) 118(3) C(10S)-C(9S)-C(8S) 119(3) C(11S)-C(10S)-C(9S) 118(4) C(12S)-C(11S)-C(10S) 123(3) C(11S)-C(12S)-C(7S) 120(3)
_______________________________________________________________________
267
VITA
Cesar Gabriel Ortiz was born in the industrious city of Monterrey, Mexico on
February 10, 1976. At the age of five, he immigrated to the United States and attended
school in Houston, TX. He graduated from John H. Reagan High School in May of
1994, and soon thereafter enrolled at Baylor University, Waco, TX. After starting his
undergraduate career in the pre-med program, he quickly realized his love for chemistry
and after five years, graduated in the spring of 1999 with a Bachelor of Science degree in
chemistry and a minor in mathematics. In June of 1999, he began his graduate career
under the guidance of Dr. Kevin Burgess and worked on the synthesis of BODIPY®
derivatives for the sequencing of DNA. After the summer of 1999, he changed research
groups and started the organometallic investigations presented herein under the direction
of Dr. Donald J. Darensbourg. Any questions or comments may be directed by
contacting his parents at: 4302 Mayfield Dr.; Houston, TX 77088; 281-999-2293.