chapter 6. group viii coordination chemistry supported by ... · group viii coordination chemistry...

161

Chapter 6 Group VIII Coordination Chemistry Supported by the

Bis(quinolinyl)amido Ligand

Portions of the following work were completed by a former postdoc in the Peters Group

Dr Baixin X Qian

162

Abstract

Entry into the group VIII chemistry of the bis(8-quinolinyl)amine (BQA 61)

ligand was effected by both protolytic and metathetical strategies The bis-ligated Fe(III)

complex [Fe(BQA)2][BPh4] (62) was prepared via amine addition to FeCl3 in the

presence of base and NaBPh4 The cation 62 is low-spin (S = frac12) and exhibits a rhombic

EPR signal (4 K X-band) Complexes featuring a single BQA ligand were prepared for

Ru and Os Reaction of the polymeric [RuCl2(cod)]n species with one equivalent of

LiBQA afforded the divalent complex (BQA)RuCl(cod) (63) while two equivalents of

LiBQA afforded the neutral congener of 62 Ru(BQA)2 (64) (cod = 14-cycloocatdiene)

Reaction of LiBQA with the phosphine containing precursors (PPh3)3MCl2 exclusively

afforded the trans-(BQA)MCl(PPh3)2 complexes (M = Ru 65 Os 66) Reaction of

HBQA with (PPh3)3MCl2 and external base (NEt3) afforded 65 for M = Ru but afforded

the isomer of 66 cis-(BQA)OsCl(PPh3)2 (67) for M = Os Complexes 63 65 and 66

were crystallographically characterized in the solid-state by X-ray diffraction Complexes

62 65 and 66 were examined for the electrochemical behavior and displayed well-

defined reversible MIIIII redox events All three species exhibit a second reversible redox

event that may be attributable to a reversible oxidation of the BQA ligand Complex 64

was compared electrochemically against the dication [(tpy)2Ru]2+ and the monocation

[(tpy)Ru(BQA)]+ (69) The RuIIIII redox couple shifts -06 V from the dication to the

monocation 69 and an additional -05 V from 69 to the neutral complex 64 Phosphine

exchange from 65 provided (BQA)RuCl(PEt3)2 (610) and (BQA)RuCl(PMe3)2 (611)

preserving the trans arrangement of the phosphine ligands Halide substitution of 611

was effected by refluxing in THF with KX salts to yield (BQA)RuBr(PMe3)2 (612) and

163(BQA)RuI(PMe3)2 (613) Metathesis reactions with 611 also yielded the hydride

(BQA)RuH(PMe3)2 (614) methyl (BQA)RuMe(PMe3)2 (615) and azide

(BQA)RuBr(PMe3)2 (616) complexes The bidentate monoanionic ligand 35-(CF3)2Ph-

QA was installed onto the (BQA)Ru platform from its sodium precursor to yield

(BQA)Ru(35-(CF3)2Ph-QA)(PPh3) (619) and its carbonyl complex (BQA)Ru(35-

(CF3)2Ph-QA)(CO) (619) Addition of a bis(phosphino)borate ligand to 65 yielded the

anionic complex [(Ph2B(CH2PPh2)2RuCl(BQA)][NEt4] (621) Treatment of 621 with

alcohol precipitated the stable five-coordinate complex (Ph2B(CH2PPh2)2Ru(BQA) 622

The addition of CO gas to 621 or 622 formed the carbonyl complex

[(Ph2BP2)Ru(CO)(BQA)] (621) Halide abstraction from 65 in the presence of a

coordinating ligand yielded the cationic complexes [(BQA)Ru(CH3CN)(PPh3)2][BPh4]

(624) [(BQA)Ru(CO)(PPh3)2][BPh4] (625) and [(BQA)Os(CO)(PPh3)2][PF6] (626)

While reaction of 65 with AgOTf resulted in the oxidized product

[(BQA)RuCl(PPh3)2][OTf] (627) Tl halide abstraction from 65 provided the dinitrogen

complexes [(BQA)Ru(N2)(PPh3)2][PF6] (630) [(BQA)Ru(N2)(PPh3)2][PF6] (631) and

[(BQA)Os(N2)(PPh3)2][PF6] (632) The latter complex was crystallographically

characterized

16461 Introduction

With the discovery of the first N2 complex of a transition metal complex in 1965

came the hope that many N2 complexes would be shortly forthcoming1 Since that

original discovery hundreds of N2 complexes have been prepared for almost every

transition metal as well as some lanthanides and actinides2 As a consequence of these

efforts the field of dinitrogen coordination chemistry is now a relatively mature one in

which many modes of N2 coordination have been identified3 complete rupture of the Nmdash

N triple bond has been observed4 and functionalization and even catalytic N2 reduction

has been achieved5 However catalytic functionalization or reduction of N2 to amine

products under mild conditions has yet to be reported

A wealth of interesting work surrounding N2 coordination chemistry has been

achieved with early and mid-transition metals particularly group VI These metal

complexes are often mid- to high-valent species and feature a wide range of ancillary

ligands Anilide and more generally amide ligands have been particularly well explored

in this context a few examples of which are shown in Figure 61 Fryzukrsquos lab has used a

diamide-bisphosphine ligand framework to demonstrate hydrogenation6 hydroboration7

and hydrosilylation8 of bound N2 on Zr and Ta On the molybdenum front the

laboratories of Cummins and Schrock have used hard anilide ligands to effect NmdashN

bond cleavage and catalytic dinitrogen reduction respectively45d These examples as

well as earlier work from the labs of Chatt9 and Hidai10 all feature metal products in their

highest oxidation states Thus either strong reductants are required to return the metal

165center to a state where dinitrogen can be bound or the metal-N species represents a

thermodynamic sink which precludes further reactivity

Figure 61 Examples of early and mid transition metal complexes employing amide

ligands Representative complexes from the labs of Cummins (left) Schrock (middle)

and Fryzuk (right)

For this reason late transition metals mdash group VIII in particular mdash have become

an attractive alternative to these early and mid-transition metal systems Late transition

metals have the ability to achieve higher oxidation states (eg M(IV-VI)) but are

commonly most stable in lower oxidation states (eg M(II-III)) which is evidenced in

their reaction chemistry Collmanrsquos group focused on synthesizing cofacial

metallodiporphyrins for the purpose of electro-catalyzed reduction of dinitrogen utilizing

late transition metals11 Although they did not succeed in reducing dinitrogen they were

able to demonstrate the complete microscopic reverse by oxidizing ammonia stepwise

back to dinitrogen (Figure 62) In an effort to demonstrate the disproportionation of a

bimetallic N2 complex (M(NequivN)Mrarr2 MequivN) Taube observed that two osmium nitrides

couple to form a half equivalent of dinitrogen upon the oxidation of [Os(NH3)5(CO)]2+12a

In later reports12bc Taubersquos group showed that the propensity for the nitride coupling is

enhanced upon substitution of the parent amine ligands for pyridine derivatives (pyridine

1662 2rsquo-bipyridine (bpy) and 22rsquo62rdquo-terpyridine (tpy)) (Figure 63) Meyerrsquos group

showed the reversible interconversion between the OsVI nitride trans-[Os(N)(tpy)(Cl)2]+

and the OsII amine complex trans-[Os(NH3)(tpy)(Cl)2]2+ (Figure 63)13 The collective

importance of this work is that ruthenium and osmium do form well-defined

characterizable intermediates along the dinitrogen reduction pathway as well as

exhibiting the desired conversion of metal nitrides to the corresponding metal amines

Figure 62 Stepwise oxidation of bound ammonia molecules in a diruthenium cofacial

porphyrin complex from Collmanrsquos laboratories

Figure 63 Chemistry observed from a [(tpy)Os(N)Cl2]Cl complex oxidative nitride

coupling (left Taube) and nitride reduction to amine (right Meyer)

167 The chemistry of late transition metal complexes with hard amido ligands has not

been thoroughly examined presumably due to a hard-soft mismatch between the ligand

and metal Interactions between the lone pair of electrons on the nitrogen and a filled d-

orbital of appropriate symmetry on the metal center destabilizes the NmdashM bond

rendering the linkage quite reactive This incompatibility can be circumvented by using

pincer ligand scaffolds where the hard functionality (eg R2N- R2C-) is attached to one

or more soft functionalities (eg R3N R3P) providing a strong chelate-effect and thereby

stabilizing the hard-soft ligand-metal mismatch14

With this in mind we set out to synthesize group VIII transition metal complexes

supported by the rigorously planar bis(8-quinolinyl)amide ligand (BQA) as a

monoanionic analog to terpyridine15 The filled amido p orbital is adjacent to a filled

metal d orbital in d6 metal complexes (Scheme 61) If significant mixing of the amido p

orbital and metal d orbital occurs the highest occupied molecular orbital (HOMO) will

be raised in energy This HOMO-raising may manifest itself at the metal complex by an

increased affinity for π-acidic ligands Herein we report our progress concerning the

coordination chemistry we have observed with this ligand scaffold on group VIII metals

including the coordination of N2

168Scheme 61

62 Results and Discussion

621 Preparation of BQA complexes of Fe Delivery of the bis(quinolinyl)amine

(HBQA 61) ligand to group 10 metals has been achieved via two routes reaction of a

metal halide with 61[Li] or reaction of the free amine 61 with metal precursor in the

presence of excess base15 Attempts to generate mono-BQA substituted Fe complexes

were unsuccessful as the bis-substituted species Fe(BQA)2 formed extensively in the

reaction mixture despite careful control of reactant stoichiometry The limited solubility

of Fe(BQA)2 prevented its thorough characterization either in solution or in the solid

state To circumvent this metalation of the BQA ligand was carried out with FeCl3

(anhydrous) via an in situ salt metathesis reaction (Eq 61) Reacting two equivalents of

the amine 61 with FeCl3 in dichloromethane with the addition of Na2CO3 in water

resulted in rapid formation of the desired complex [Fe(BQA)2][Cl] Addition of an

aqueous solution of NaBPh4 to the reaction afforded [Fe(BQA)2][BPh4] (62) The

resulting brick red cationic FeIII species is air stable and is readily soluble in polar

solvents (CH2Cl2 DMSO) unlike the insoluble neutral Fe(BQA)2 species Complex 62

169exhibits paramagnetically shifted 1H NMR resonances and features a doublet ground state

(microeff = 21 BM) as determined by the Evans method16 indicating the Fe nucleus is low-

spin

A dichloromethane solution of 62 exhibits multiple intense transitions in the UV-

visible region [λmaxnm (εM-1cm-1)] 1030(11000) 680(2700) 514(33000) 418(49000)

306(90000) (Fig 1) The high extinction coefficients for the intense transitions at 514

418 and 306 nm are most likely ligand based π-π transitions which is in agreement

with the spectrum published for [Co(BQA)2][ClO4] by Lahiri17 However the presence of

a weak transition at 680 nm may be the d-d transition (3A1rarr2Tg) for the d5 system The

large extinction coefficient for the band at 1030 nm suggests it is a charge transfer band

quite possibly a LMCT event where a ligand based electron is excited into the singly-

occupied d orbital

The EPR of a solid sample of 62 was also collected at 4 K shown in Figure 62

The spin S = frac12 state of 62 gives rise to a rhombic signal where the three g tensors are

resolved gz = 239 gy = 214 gx = 198 No hyperfine coupling to nitrogen is observed

170

Figure 64 Electronic spectrum of [Fe(BQA)2][BPh4] (62) inset highlights spectrum

from 650-750 nm

Figure 65 EPR spectrum of solid 62 (4K X-band 962 GHz)

622 Preparation of BQA complexes of Ru and Os In contrast to metalation with Fe

a single BQA ligand can be installed onto divalent Ru or Os from a variety of precursors

171For example reaction of the polymeric [RuCl2(cod)]n with one equivalent of 61[Li]

yielded (BQA)RuCl(COD) (63) and variable amounts of the di-substituted species

Ru(BQA)2 (Eq 62) (cod = cyclooctadiene) Flash chromatography effectively separated

the products Complex 63 has been characterized in the solid-state by X-ray

crystallography and its solid-state structure is shown in Figure 63 Quantitative

conversion to the di-substituted species Ru(BQA)2 (64) was achieved by refluxing

[RuCl2(COD)]n with two equivalents of 61[Li] in toluene An electrospray mass

spectrum (ESMS) of the product mixture reveals only the parent ion peak for the

disubstituted species 64 at mz = 642 without 63 or any ligand fragmentation apparent

in the spectrum

172

Figure 66 Displacement ellipsoid representation (50) of (left) (BQA)RuCl(cod) (63)

(center) (BQA)RuCl(PPh3)2 (65) and (right) (BQA)OsCl(PPh3)2 (66) Hydrogen atoms

have been removed for clarity Selected bond distances (Aring) and angles (ordm) for 63 Ru-N1

2128(3) Ru-N2 2048(2) Ru-N3 2126(3) Ru-Cl 2426(1) avg Ru-C 2215(3) N1-Ru-

N2 769(1) N2-Ru-N3 779(1) N1-Ru-N3 1515(1) for 65 Ru-N1 2066(3) Ru-N2

2005(2) Ru-N3 2061(3) Ru-Cl 2482(1) Ru-P1 2397(1) Ru-P2 379(1) N1-Ru-N2

804(1) N2-Ru-N3 803(1) N1-Ru-N3 1607(1) P1-Ru-P2 1789(1) for 66 Os-N1

2063(3) Os-N2 2023(3) Os-N3 2064(3) Os-Cl 2488(1) Os-P1 2368(1) Os-P2

381(1) N1-Os-N2 815(1) N2-Os-N3 801(1) N1-Os-N3 1615(1) P1-Os-P2 1748(1)

173

Refluxing RuCl2(PPh3)3 in dichloromethane with the free amine of BQA in the

presence of excess base (NEt3) resulted in the formation of (BQA)RuCl(PPh3)2 (65)

which can be isolated in crystalline yields exceeding 85 (Eq 63) The 31P NMR

spectrum of 65 shows a single chemical shift at δ = 29 ppm in benzene suggesting the

phosphorus nuclei are trans-disposed with the BQA ligand bound in a mer fashion

Product 65 can also be obtained via reaction of 61[Li] and RuCl2(PPh3)3 in toluene at

room temperature Similarly the Os congener (BQA)OsCl(PPh3)2 (66) can be formed via

reaction of 61[Li] and OsCl2(PPh3)3 in toluene at room temperature However in

reacting OsCl2(PPh3)3 with the free amine 61 in the presence of excess triethylamine

base the cis-product of 66 cis-(PPh3)2OsCl(BQA) (67) is obtained exclusively as

indicated by the 31P NMR spectrum (δ 22 -09 2JP-P = 107 Hz) (Eq 63) While 67 can

be isolated as a brown solid attempts to crystallize this species exclusively yielded

crystals of the green trans-disposed product 66 Solid-state crystal structures for

complexes 65 and 66 are shown in Figure 66 The solid-state structures for 63 65 and

66 all demonstrate that the BQA ligand binds in a mer-fashion The amido N-M bond

distances are consistently shorter (∆ = 006 Aring) than the quinolinyl N-M bond distances

The proclivity for the BQA ligand to pinch back is also apparent by the N1-M-N3 bond

angles which range from 150-160ordm

174

623 Electrochemical Analysis of (BQA)nM Complexes It is interesting to compare

the FeIIIII redox potentials of 62 to other examples of homoleptic Fe complexes Figure

67 shows the cyclic voltammogram of 62 in 01M nBu4NPF6 in dichloromethane and

referenced against an internal FcFc+ standard The FeIIIII couple for 62 (Efrac12 = -079 V

∆p = 65 mV) is 079 V more reducing than the FeIIIII couple for Fc suggesting 62 could

be used as a mild oxidizing agent18 The electron-releasing amides are more reducing

than even Cp2Fe which exhibits an FeIIIII couple at -048 V18 In addition to the FeIIIII

couple complex 62 exhibits a second quasi-reversible redox event at Efrac12 = +014 V

The shape of the secondary oxidation event was independent of scan rate (005-05 Vs)

and did not change noticeably when THF or dichloromethane was the solvent This

second redox event could signify a quasi-reversible FeIVIII redox event or it could

represent some redox process taking place on the BQA ligand itself The BQA ligand

which exhibits an irreversible oxidation event at +056 V (vs FcFc+)17 is most likely the

candidate for oxidation in this case If this second redox event is in fact ligand based the

radical can easily be delocalized over the quinoline rings of BQA The contributing

resonance structures are presented in Scheme 62

175

Figure 67 Cyclic voltammetry of 62 in 04 M nBu4NPF6THF scan rate = 75 mVs

Scheme 62

In addition to the iron complexes a series of ruthenium complexes bearing the

BQA ligand and 22rsquo2rdquo-terpyridine (tpy) ligands were synthesized to further assess the

BQA ligandrsquos electron releasing character [Ru(tpy)2]2+ (68)19 [(terpy)Ru(BQA)][BPh4]

(69) and Ru(BQA)2 (64) Terpyridine was chosen as a coligand to maintain a

nitrogenous donor sphere and because of its structural resemblance to BQA Complex 69

was synthesized by refluxing a dichloromethane solution of (tpy)RuCl2(PPh3)20 with one

176equivalent of NaBPh4 and 61 in the presence of three equivalents of triethylamine The

cyclic voltammograms for 68 69 and 64 are presented in Figure 68 The

measurements were taken in 01M nBu4NPF6 in dichloromethane and referenced against

an internal FcFc+ standard Complexes 68 69 and 64 all exhibit reversible RuIIIII

couples labeled (A) (B) and (C) in Fig 68 respectively The RuIIIII couple shifts -062

V going from the dication 68 (Efrac12 = 092 V)19 to the monocation 69 (Efrac12 = 031 V ∆p =

89 mV) and the RuIIIII couple shifts an additional -052 V going from 69 to neutral 64

(Efrac12 = -021 V ∆p = 99 mV) Like complex 62 neutral 64 exhibits a second reversible

wave centered at Efrac12 = +060 V (∆p = 97 mV) This event may be attributable to a

reversible RuIVIII redox event or may represent a reversible oxidation of the BQA ligand

like that observed for 62 The latter scenario is the more likely

Figure 68 Cyclic voltammetry of (top) [(tpy)2Ru]2+ (68) (middle) [(tpy)Ru(BQA)]+

(69) (bottom) Ru(BQA)2 (64) in 04 M nBu4NPF6CH2Cl2 scan rate = 75 mVs

177 The potential MIIIIV redox couples observed for 62 and 64 prompted us to

examine whether this feature was limited to complexes of the composition M(BQA)2

Interestingly both the ruthenium and osmium complexes 65 and 66 exhibit two

reversible redox processes as shown in Figure 69 (04 M nBu4NPF6 in dichloromethane

referenced to internal FcFc+) Complex 65 exhibits a reversible redox wave at Efrac12 = -

055 V (∆p = 78 mV) assigned as the RuIIIII couple The second reversible redox wave

comes at Efrac12 = +045 V (∆p = 76 mV) and is assigned as a reversible BQA oxidation

event This second redox couple is close to the second redox couple observed for

complex 64 (Efrac12 = +060 V) The Os complex 66 similarly displays two reversible redox

processes centered at Efrac12 = -072 V (OsIIIII ∆p = 85 mV) and Efrac12 = +023 V (BQABQA+

∆p = 83 mV) The reversible nature of the second redox couple observed for 64 65 and

66 suggests that they are metal based redox events whereas the irreversible nature of

the second redox event for 62 indicates a ligand-centered oxidation mechanism is more

likely

178

Figure 69 Cyclic voltammetry of (top) (BQA)RuCl(PPh3)2 (65) and (bottom)

(BQA)OsCl(PPh3)2 (66) in 01 M nBu4NPF6CH2Cl2 scan rate = 50 mVs

624 Ligand Exchange Reactions To survey the general reactivity of the

(BQA)MX(PPh3)2 complexes we probed the exchange reactions of the phosphine and

halide ligands (Scheme 63) Substitution of the PPh3 units on 65 for smaller stronger σ-

donor phosphine ligands occurs under relatively mild conditions Triethylphosphine

substitutes twice at 40 ordmC to form trans-(BQA)RuCl(PEt3)2 (610) while

trimethylphosphine substitutes at room temperature to form trans-(BQA)RuCl(PMe3)2

(611) (Scheme 63) The trans geometry is preserved from 65 as evidenced by the 31P

NMR which shows a single chemical shift for both 610 and 611 at 118 and 05 ppm

respectively Refluxing 65 in excess pyridine resulted in incomplete phosphine

substitution as ascertained by 31P NMR while acetonitrile does not affect any phosphine

displacement under refluxing conditions Likewise refluxing precursor 65 with larger

179ligand types like PCy3 or N-heterocyclic carbenes did not result in any phosphine

displacement

Scheme 63

One of the questions concerning the BQA ligand moiety was whether the amido

nitrogen would display any trans-influence in octahedral complexes Thus we probed

replacing the halide ligand in 611 with a range of anionic ligands to determine the effect

of having the amido nitrogen trans to the X-type ligand Refluxing 611 in THF with 4

equivalents of the appropriate potassium salt achieved substitution of the halide ligand to

produce the bromide and iodide complexes trans-(BQA)RuBr(PMe3)2 (612) and trans-

180(BQA)RuI(PMe3)2 (613) (Scheme 63) Reacting 611 with LiAlH4 in toluene at room

temperature provided the hydride trans-(BQA)RuH(PMe3)2 (614) in moderate yield

while synthesis of the methyl complex trans-(BQA)RuMe(PMe3)2 (615) required excess

MeLi in refluxing toluene The azide complex trans-(BQA)Ru(N3)(PMe3)2 (616) was

prepared by refluxing NaN3 and 611 in a mixture of THF and dichloromethane for

several hours Complexes 612-616 all maintain the coordination environment of the

parent species 611 showing no propensity to redistribute the X-type ligands as a result

of the trans-influence from the BQA amido nitrogen to leave the strong trans-influencing

ligands cis-disposed21

Contrary to this trend observed above reaction of 65 with the sodium salt of the

monoquinolinyl-amide [35-(CF3)2Ph-QA][Na(Et2O)] (618) resulted in formation of the

deep purple complex (BQA)Ru(35-(CF3)2Ph-QA)(PPh3) (619) (Scheme 64) For 619

the amide from the mono-quinoline ligand is trans to the phosphine ligand orienting the

bulky bis-35-triflouromethyl phenyl amide substituent on the opposite side of the BQA

plane from the phosphine ligand This orientation was verified via crystallographic

characterization of 619 whose solid-state structure is shown in Figure 610 Phosphine

ligand substitution only occurred when 619 was refluxed in toluene For example the

carbonyl adduct (BQA)Ru(35-(CF3)2Ph-QA)(CO) (620) could only be formed by

refluxing 619 in toluene under an atmosphere of CO gas for 20 hours Formation of 620

from 619 was accompanied by a color change from deep purple to an intense red

181Scheme 64

Reaction of 65 with the anionic bis-phosphine [Ph2B(CH2PPh2)2][NEt4] (hereafter

referred as [Ph2BP2])22 in THF generated the product [(Ph2BP2)RuCl(BQA)][NEt4] (621)

as a midnight blue solid The 31P NMR for complex 621 displays a doublet of doublets (δ

54 283 ppm 2JP-P = 36 Hz) indicating the phosphorous inequivalent environments as

confirmed by a solid state X-ray diffraction study (Figure 610) Installation of the

[Ph2BP2]- ligand affected complete displacement of the phosphine ligands from 65

though the chloride remains bound to the metal cis to the amido nitrogen Washing 621

with ethanol abstracted an equivalent of NEt4Cl and precipitated the 16 e- neutral

complex (Ph2BP2)Ru(BQA) (622) as a wine red solid (Scheme 65) Complex 622

displayed a singlet in the 31P NMR at 69 ppm indicating the equivalent phosphine

positions with 622 adopting trigonal-bipyramidal geometry Complex 622 is stable as a

coordinatively-unsaturated complex and does not pick up an equivalent of dinitrogen to

fill the vacant coordination site even under elevated pressures (60-80 psi) However the

carbonyl complex (Ph2BP2)Ru(CO)(BQA) (623) was readily prepared by addition of CO

gas to a solution of 622 in dichloromethane or alternatively by chloride displacement in

621 in THF

182

Figure 610 Displacement ellipsoid representation (50) of (left) (BQA)Ru(35-

(CF3)2Ph-QA)(PPh3) (619) and (right) [(Ph2BP2)RuCl(BQA)][NEt4] (621) Hydrogen

atoms and solvent molecules have been removed for clarity Selected bond distances (Aring)

and angles (ordm) for 619 Ru-N1 2066(3) Ru-N2 2021(3) Ru-N3 2045(3) Ru-N4

2094(3) Ru-N5 2144(3) Ru-P1 2319(1) N1-Ru-N2 8102(1) N2-Ru-N3 8088(1) N1-

Ru-N3 16082(1) N4-Ru-N5 7748(1) N5-Ru-P1 17099(1) for 621 Ru-N1 2095(4)

Ru-N2 2050(4) Ru-N3 2078(4) Ru-Cl 2515(1) Ru-P1 2353(1) Ru-P2 2291(1) N1-

Ru-N2 789(1) N2-Ru-N3 798(1) N1-Ru-N3 1581(1) P1-Ru-P2 9033(5)

183Scheme 65

625 Formation of Cationic Species An alternative route to opening the coordination

sphere of the Ru and Os complexes was to remove the halide ligands from complexes 65

and 66 Salt metathesis on 65 or 66 with simple sodium or potassium reagents (eg

NaBPh4 or KPF6) was not observed in the absence of a strongly binding ligand Reaction

of 65 with NaBPh4 in a mixture of THFacetonitrile immediately produced the purple

solvento species [(BQA)Ru(NCCH3)(PPh3)2][BPh4] (624) with concomitant production

of NaCl (Scheme 66) However complex 65 was unreactive with an excess of NaBPh4

under a dinitrogen atmosphere over a period of several days The observed reactivity did

not change even under elevated pressures (14-80 psi) of N2 nor did it change using a

variety of solvents (THF THFEtOH CH2Cl2) In contrast reaction of 65 and NaBPh4

under an atmosphere of carbon monoxide in THF produces the cherry red complex

[(BQA)Ru(CO)(PPh3)2][BPh4] (625) within minutes (Scheme 66) The Os congener

[(BQA)Os(CO)(PPh3)2][BPh4] (626) was similarly synthesized from 66 and NaBPh4

184For both 625 and 626 the phosphines remain trans-disposed as indicated by their 31P

NMR which show single peaks for both species (δ = 301 ppm for 625 031 ppm for

626) The infrared stretching frequency of the carbonyl ligand for cationic 625 (νCO =

1946 cm-1) is lower than that of the neutral terpyridine complex (trpy)RuCl2(CO) (νCO =

1953 cm-1)20 The Os complex 626 features a reduced carbonyl stretching frequency (νCO

= 1921 cm-1) from 625

Scheme 66

In an effort to synthesize a dinitrogen complex of Ru or Os more aggressive

halide scavenging reagents were tried Puenta et al successfully employed AgOTf as a

halide scavenger to form a cationic dinitrogen complex en route to

[TpRu(N2)(PEt3)2][BPh4] (Tp = hydrotris(pyrazolyl)borate)23 Van Koten successfully

produced the pincer complex [RuII(OTf)C6H2(CH2PPh2)2(PPh3)] using AgOTf with the

corresponding chloride precursor24 In an attempt to facilitate a similar transformation

from 65 a solution of 65 in THF was reacted with an equimolar amount of AgOTf in

the dark The initial aqua-blue hue of 65 immediately faded as a dark brown precipitate

formed with concomitant formation of Ag0 The isolated brown solid was identified as

185the oxidized product [(BQA)RuIIICl(PPh3)2][OTf] (627) (Scheme 66) Oxidation of the

Ru center is kinetically favored over halide-abstraction

To circumvent this undesirable oxidation event Tl reagents were then

investigated to facilitate the halide abstraction The MII triflate complexes

(BQA)Ru(OTf)(PPh3)2 (628) and (BQA)Os(OTf)(PPh3)2 (629) were readily afforded by

reaction of the corresponding chloride complexes 65 and 66 with TlOTf in THF

(Scheme 67) These complexes could not be isolated as single complexes because the

triflate ligand showed a propensity to dissociate Upon reacting 65 with TlPF6 in a THF

solution the color of the solution darkened within minutes to produce a midnight blue

solution with concomitant formation of a white precipitate The 31P NMR of this solution

taken in situ shows a very modest shift from 65 (δ = 29 ppm) to 28 ppm whereas the

solution IR did not reveal any different vibrational intensities from the parent species 65

Removal of the volatiles in vacuo yielded a purple solid that had limited solubility in

THF and was completely insoluble in hydrocarbon solvents The purple solids readily

dissolved in dichloromethane to give an intense cherry-red solution (λmax = 542 nm) The

solution IR of the red solution displayed an intense vibration at 2130 cm-1 which was

attributed to a dinitrogen molecule binding trans to the BQA amido nitrogen in the

complex [(BQA)Ru(N2)(PPh3)2][PF6] (630) Complex 630 shows a single 31P NMR

resonance at 25 ppm shifted upfield from the parent species 65 The purple intermediate

that preceded formation of 630 has been postulated as a solvento species where THF

binds in place of the Cl The THF complex has not been completely characterized due to

its propensity to form 630 upon storage under N2 atmospheres Thallium halide

abstraction from the PMe3 complex 611 with TlPF6 proceeded directly to a dinitrogen

186adduct complex [(BQA)Ru(N2)(PMe3)2][PF6] (631) even in THF solutions (KBrTHF

νNN = 2129 cm-1) without an observable solvento intermediate Reaction of the Os

complex 66 with TlPF6 likewise produced the dinitrogen adduct

[(BQA)Os(N2)(PPh3)2][PF6] (632) with no observable THF-solvent adduct intermediate

(Scheme 67) The Os congener 632 is remarkably stable and even identifiable as the

OsmdashN2 cation via electrospray mass-spectrometry We obtained a solid state structure

via X-ray crystallography which confirms the N2 molecule is trans to the amido nitrogen

(Figure 611) The N2 ligand does not exhibit any elongation from free N225 indicative

that the N2 is not being activated by Os2+ which is also evident from the high stretching

frequency (υNN = 2071 cm-1) observed for 632

Scheme 67

187

Figure 611 Displacement ellipsoid representation (50) of [(BQA)Os(N2)(PPh3)2][PF6]

(632) Hydrogen atoms have been removed for clarity Selected bond distances (Aring) and

angles (ordm) for 632 Os-N1 2096(2) Os-N2 2032(3) Os-N3 2062(2) Os-N4 1954(3)

N4-N5 1080(4) Os-P1 2403(1) Os-P2 2403(1) N1-Os-N2 7997(1) N2-Os-N3

8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions

The coordination chemistry of group VIII complexes supported by the

bis(quinolinyl)amide (BQA) ligand has been explored While only a bis-ligated complex

of Fe could be isolated both Ru and Os BQA complexes show a large degree of ligand

substitution chemistry Electrochemical analyses of these complexes indicate that the

high-energy amido lone pair may be exhibiting reversible oxidation chemistry The

(BQA)Ru core undergoes facile phosphine substitution as well as halide exchange

reactions Methathetic routes yielded (BQA)Ru complexes featuring hydrides azides and

even methyl ligands Formation of Ru and Os cationic species by halide abstraction

188provided convenient entry routes to carbonyl and dinitrogen complexes While the π-

acidic ligands prefer a trans-disposition to the BQA amido nitrogen the stretching

frequencies for the CO and N2 ligands measured by IR do not indicate a substantial

degree of π back-donation from the metal center Thus our original hypothesis that

having the amido lone pair adjacent to a filled metal d orbital (of appropriate symmetry)

would raise the complex HOMO to facilitate interactions with π-acidic ligands may not

be occurring to a large extent Because the (BQA)Ru and (BQA)Os complexes are

excellent synthons for ligand-exchange reactions these may be candidates to facilitate

group transfer chemistry such as epoxidation cyclopropanation or aziridination

chemistry from azide precursors

189

Table 61 X-ray diffraction experimental details for (BQA)RuCl(cod) (63) (BQA)RuCl(PPh3)2 (65) (BQA)OsCl(PPh3)2 (66)

(BQA)Ru(35-(CF3)2Ph-QA)(PPh3) (619) [(Ph2B(CH2PPh2)2)RuCl(BQA)][NEt4] (621) and [(BQA)Os(N2)(PPh3)2][PF6] (632)

63 65 66middotC6H6 619 621middot2 CH2Cl2middot THF 632 Chemical Formula

C32H30ClN3 Ru C54H41ClN3P2Ru C60H48ClN3OsP2 C53H36F6N5PRu C70H78BCl5N4O2P2Ru C54H42F6N5OsP3

Formula Weight 59311 93036 109860 98891 134243 115804

T (ordmC) 177 177 177 177 177 177 λ (Aring) 071073 071073 071073 071073 071073 071073 a (Aring) 11570(3) 105631(9) 15009(5) 18610(5) 119746(11) 117356(9) b (Aring) 20291(6) 185043(16) 21087(7) 12525(3) 127722(12) 134605(10) c (Aring) 21838(6) 218173(18) 15205(5) 17854(5) 22031(2) 167482(13) α (ordm) 90 90 90 90 102928(2) 85072(1) β (ordm) 90 90775(2) 101351(5) 93307(4) 97964(2) 72800(1) γ (ordm) 90 90 90 90 94613(2) 64240(1)

V (Aring3) 5127(2) 42641(6) 4718(3) 4178(2) 32307(5) 22734(3) Space Group Pbca P2(1)n P2(1)n Cc P-1 P-1

Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692

micro (cm-1) 743 548 2872 487 546 2981 R1 wR2 (Igt2σ(I))

00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642

R1 = Σ ||Fo|-|Fc|| Σ |Fo| wR2 = Σ[w(Fo2-Fc

2)2]Σ[w(Fo2)2]12

190

64 Experimental Section

641 General Considerations All manipulations were carried out using standard

Schlenk or glove-box techniques under a dinitrogen atmosphere Unless otherwise noted

solvents were deoxygenated and dried by thorough sparging with N2 gas followed by

passage through an activated alumina column Non-halogenated solvents were typically

tested with a standard purple solution of sodium benzophenone ketyl in tetrahydrofuran

in order to confirm effective oxygen and moisture removal The reagents NaBPh4 TlPF6

FeCl2 and FeCl3(anhydrous) were purchased from commercial vendors and used without

further purification HBQA (61 HBQA = bis(quinolinyl)amide)15 RuCl2(PPh3)326

[RuCl2(cod)]n27 OsCl2(PPh3)328 and [Ph2B(CH2PPh2)2][NEt4]22 were synthesized as

described previously Deuterated solvents were degassed and stored over activated 3-Aring

molecular sieves prior to use Elemental analyses were carried out at Desert Analytics

Tucson Arizona NMR spectra were recorded at ambient temperature on Varian Mercury

300 MHz Joel 400 MHz and an Anova 500 MHz spectrometers unless otherwise noted

1H and 13C NMR chemical shifts were referenced to residual solvent 31P NMR 11B

NMR and 19F NMR chemical shifts are reported relative to an external standard of 85

H3PO4 neat BF3middotEt2O and neat CFCl3 respectively IR spectra were recorded on a Bio-

Rad Excalibur FTS 3000 spectrometer controlled by Win-IR Pro software MS data for

samples were obtained by injection of a hydrocarbon solution into a Hewlett Packard

1100MSD Mass Spectrometer (ES+) or an Agilent 5973 Mass Selective Detector (EI)

UV-vis measurements were taken on a Hewlett Packard 8452A diode array spectrometer

using a quartz crystal cell with a Teflon cap X-ray diffraction studies were carried out in

191the Beckman Institute Crystallographic Facility on a Bruker Smart 1000 CCD

diffractometer

642 X-ray Crystallography Procedures X-ray quality crystals were grown as

indicated in the experimental procedures for each complex The crystals were mounted

on a glass fiber with Paratone-N oil Structures were determined using direct methods

with standard Fourier techniques using the Bruker AXS software package In some

cases Patterson maps were used in place of the direct methods procedure

643 EPR Measurements X-band EPR spectra were obtained on a Bruker

EMX spectrometer equipped with a rectangular cavity working in the TE102 mode

Variable temperature measurements were conducted with an Oxford continuous-flow

helium cryostat (temperature range 36-300 K) Accurate frequency values were provided

by a frequency counter built in the microwave bridge Solution spectra were acquired in

toluene for all of the complexes Sample preparation was performed under a nitrogen

atmosphere

644 Syntheses of Compounds

Synthesis of [Fe(BQA)2][BPh4] (62) HBQA (082 g 302 mmol) and FeCl3

(anhydrous) (245 mg 15 mmol) were added to a vigorously stirring solution of CH2Cl2

A solution of Na2CO3 (320 mg 305 mmol) and NaBPh4 (517 mg 15 mmol) in H2O (30

mL) was added to the CH2Cl2 solution The reaction solution was stirred for 20 h at room

temperature The product was extracted into CH2Cl2 and washed with H2O (3 x 25 mL)

The organic phase was evaporated to dryness to yield a red powder (098 g 71) 1H

NMR (DMSO-d6 300 MHz 25degC) δ 291 198 717 691 (t J = 66 Hz) 677 (t J =

66 Hz) -83 -290 -617 -653 UV-Vis region [λmaxnm (εM-1cm-1)] 1030(11000)

192680(2700) 514(33000) 418(49000) 306(90000) ES-MS (Electrospray) positive mode

[(BQA)2Fe]+ mz 596 found (M)+ mz 596 [Ph4B]- mz 319 found (M)- mz 319 Anal

Calcd for C60H44BFeN6 C 7545 H 458 N 1112 found C 7522 H 468 N 1100

Synthesis of (BQA)RuCl(COD) (63) A suspension of Ru(COD)Cl2 (036 g 13

mmol) in toluene (10 mL) was treated with a solution of [BQA][Li] (035 g 13 mmol) in

toluene (10mL) at room temperature After the mixture was stirred for 48 h the solvent

was removed in vacuo The residue was extracted with dichloromethane and filtered

through Celite on a sintered glass frit to yield a purple filtrate Layering the filtrate with

petroleum ether precipitated a purple solid The product was collected via filtration

washed with copious amounts of petroleum ether and dried in vacuo (041 g 62) 1H

NMR (CDCl3 300 MHz) δ 912ndash911 (m 2H) 812ndash809 (m 2H) 790ndash787 (m 2H)

748ndash737 (m 2H) 701ndash698 (m 2H) 452ndash450 (m 2H) 319ndash317 (m 2H) 267ndash260

(m 2H) 229 ndash220 (m 2H) 196 ndash192 (m 2H) 180 ndash174 (m 2H) 13C 1H NMR

(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352

11285 9475 8992 3039 2868 UV-Vis region [λmaxnm (εM-1cm-1)] 324 (9900)

302 (7000) 590 (6200) Anal Calcd for C26H24ClN3Ru C 6064 H 470 N 816 found

C 6073 H 482 N 789

Synthesis of Ru(BQA)2 (64) A suspension of Ru(COD)Cl2 (036 g 13 mmol)

in toluene (10 mL) was added to a solution of [BQA][Li] (072 g 132 mmol) in toluene

(10mL) in a bomb reactor with a Teflon stopcock The mixture was heated at reflux for

48 h The volatiles were removed in vacuo and the residue was extracted with

dichloromethane and filtered through Celite on a sintered glass frit to yield a red-purple

filtrate Layering the filtrate with petroleum ether precipitated a burgundy solid The

193product was collected via filtration washed with copious amounts of petroleum ether and

dried in vacuo (152 g 89) 1H NMR (CD2Cl2 300 MHz 25degC) δ 910 (dd J = 48 Hz

15 Hz 4H) 716 (d J = 78 Hz 4H) 705 (t J = 81 Hz 4H) 665 (d J = 78 Hz 8H)

635 (dd J = 48 Hz 15 Hz 4H) 13C 1H NMR (CD2Cl2 75 MHz) δ 150 138 132

129 1284 1228 122 Anal Calcd for C36H24N6Ru C 6738 H 377 N 1310 found

C 6763 H 366 N 1312

Synthesis of trans-(BQA)RuCl(PPh3)2 (65) A solution of HBQA (500 mg 184

mmol) and NEt3 (373 mg 369 mmol) in CH2Cl2 (5 mL) was added to a stirring solution

of RuCl2(PPh3)4 (225 g 184 mmol) in CH2Cl2 (8 mL) The reaction solution was heated

to 65ordmC for 5h The reaction was then cooled to room temperature and the solvent

removed in vacuo The green solid was washed with ethanol (2 x 15 mL) Et2O (2 x 15

mL) and petroleum ether (2 x 15 mL) The remaining solid was dried in vacuo yielding

121 g of 65 (702) Crystals of (BQA)RuCl(PPh3)2 were grown by vapor diffusion of

petroleum ether into benzene 1H NMR (C6D6 300 MHz 25degC) δ 9036 (dd J = 48 Hz

15 Hz 2H) 749 (m 12H) 708 (d J = 78 Hz 2H) 696 (t J = 81 Hz 2H) 675-687

(m 20 H) 653 (d J = 78 Hz 4H) 640 (dd J = 48 Hz 15 Hz 4H) 31P 1H NMR

(C6D6 1214 MHz 25degC) δ 292 ES-MS (Electrospray) calcd for C54H42ClN3P2Ru (M)-

mz 931 found (M+H) mz 931 669 (M-PPh3) Anal Calcd for C54H42ClN3P2Ru C

6963 H 455 N 451 found C 6893 H 469 N 449

Synthesis of trans-(BQA)OsCl(PPh3)2 (66) A solution of [BQA][Li] (300 mg

111 mmol) in toluene (5 mL) was added to a stirring solution of OsCl2(PPh3)4 (1156 g

111 mmol) in toluene (8 mL) at room temperature The reaction solution was heated to

65 ordmC for 5h The reaction was then cooled to room temperature and the volatiles were

194removed in vacuo The green solid was washed with ethanol (2 x 15 mL) Et2O (2 x 15


104 g of analytically pure material (92) Crystals of 66 were grown by vapor diffusion

of petroleum ether into benzene 1H NMR (CD2Cl2 300 MHz 25degC) δ 844 (dd J = 48

Hz 15 Hz 2H) 762 (m 12H) 708 (d J = 78 Hz 2H) 694 (t J = 82 Hz 2H) 675-

687 (m 20 H) 648 (d J = 78 Hz 4H) 638 (dd J = 48 Hz 15 Hz 4H) 31P 1H

NMR (C6D6 1214 MHz 25degC) δ -8 ES-MS (Electrospray) calcd for C54H42ClN3P2Os

(M) mz 1020 found (M+H) mz 1021 986 (M-Cl) Anal Calcd for C54H42ClN3P2Os C

6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410

Synthesis of cis-(BQA)OsCl(PPh3)2 (67) A solution of HBQA (500 mg 184


of OsCl2(PPh3)3 (193 g 184 mmol) in CH2Cl2 (8 mL) The reaction solution was heated

to 65ordmC for 5h The reaction was then cooled to room temperature and the volatiles were

removed in vacuo The brown solid was washed with ethanol (2 x 15 mL) Et2O (2 x 15


126 g of 67 (67) Vapor diffusion of petroleum ether into a solution of 67 in benzene

yielded crystals of the trans-product 66 1H NMR (C6D6 300 MHz 25degC) δ 88 (dd J =

48 Hz 15 Hz 2H) 76-65 (m 36 H) 640 (dd J = 48 Hz 15 Hz 4H) 31P 1H

NMR (C6D6 1214 MHz 25degC) δ 22 (d J = 107 Hz) -092 (d J = 107 Hz) ES-MS

(Electrospray) calcd for C54H42ClN3P2Os (M)+ mz 1020 found (M+H) mz 1021 986

(M-Cl)

Synthesis of [(tpy)Ru(BQA)][BPh4] (69) A solution of HBQA (326 mg 012


195of (tpy)RuCl2(PPh3) (50 mg 0075 mmol) and NaBPh4 (15 mg 0075 mmol) in ethanol

(5 mL) at room temperature The reaction solution was then heated at 65 ordmC for 15h The

reaction mixture was then cooled to room temperature and the volatiles were removed in

vacuo The red solid was washed with Et2O (2 x 15 mL) and petroleum ether (2 x 15

mL) The remaining solid was dried in vacuo yielding 596 mg of analytically pure

material (86) ES-MS (Electrospray) calcd for C33H23N6Ru (M)+ mz 605 found (M+)

mz 605 Anal Calcd for C57H43BN6Ru C 7410 H 469 N 910 found C 7435 H

475 N 906

Synthesis of trans-(BQA)RuCl(PEt3)2 (610) A blue solution of 65 (015 g

047 mmol) in toluene (10 mL) was treated with neat triethylphosphine (020 mL 20

mmol) at room temperature The mixture was heated to reflux for 18 h The reaction

mixture was cooled down and all volatile materials were removed in vacuo The green

solids were washed with Et2O (3 x 15 mL) and petroleum ether (3 x 15 mL) The

remaining green solid was dried in vacuo to yield analytically pure material (0073 g

70) 1H NMR (C6D6 300 MHz) δ 906 (dd J = 48 Hz 15 Hz 4H) 718 (d J = 78

Hz 4H) 704 (t J = 82 Hz 4H) 672 (d J = 78 Hz 8H) 640 (dd J = 48 Hz 15 Hz

4H) 182 (m 12 H) 070 (d 18H) 31P1H NMR (C6D6 121 MHz) δ 118 Anal Calcd

for C30H42ClN3P2Ru C 5602 H 658 N 653 Found C 5588 H 648 N 651

Synthesis of trans-(BQA)RuCl(PMe3)2 (611) A blue solution of 65 (044 g

047 mmol) in THF (10 mL) was treated with neat trimethylphosphine (019 mL 19

mmol) at ndash30 degC The mixture was allowed to warm to room temperature during which

time the solution turned green After the mixture was stirred at room temperature for 1 h

all volatile materials were removed in vacuo Flash column chromatography with 41

196tolueneethyl acetate yielded black purple analytically pure solid (018 g 69) (Rf =

021) 1H NMR (C6D6 300 MHz) δ 906ndash903 (m 2H) 770ndash767 (m 2H) 734ndash722 (m

4H) 674ndash672 (m 2H) 658ndash653 (m 2H) 068 (t J = 30 Hz 18H) 13C1H NMR

(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR

(C6D6 121 MHz) δ 047 ES-MS (Electrospray) calcd for C24H30ClN3P2Ru (M)+ mz

559 found (M+) mz 559 Anal Calcd for C24H30ClN3P2Ru C 5157 H 541 N 752

Found C 5166 H 535 N 743

Synthesis of trans-(BQA)RuBr(PMe3)2 (612) A green solution of 611 (013 g

023 mmol) in 4 mL THFMeOH (11) was mixed with potassium bromide (90 mg 076

mmol) at room temperature The mixture was heated to 50 degC for 4 h cooled and filtered

over a pad of Celite The filtrate was dried in vacuo then redissolved in toluene and

flashed through silica gel The volatiles were removed in vacuo to yield a purple solid

The purple product was washed with petroleum ether (2 x 15 mL) and dried in vacuo

(011 g 77) 1H NMR (C6D6 300 MHz) δ 919ndash917 (m 2H) 770ndash767 (m 2H) 730ndash

722 (m 4H) 673ndash670 (m 2H) 653ndash648 (m 2H) 072 (t J = 30 Hz 18H) 13C1H

NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812

12202 11366 11341 1154 (t J = 115 Hz) 31P1H NMR (C6D6 121 MHz) δ ndash094

Anal Calcd for C24H30BrN3P2Ru C 4777 H 501 N 696 Found C 5072 H 530 N

650

Synthesis of trans-(BQA)RuI(PMe3)2 (613) A green solution of 611 (89 mg

016 mmol) in 4 mL THFMeOH (11) was mixed with potassium iodide (90 mg 054

mmol) at room temperature The mixture was heated at 50 degC for 4 h filtered over a pad

197of Celite and the volatiles removed in vacuo to yield a purple solid The filtrate was dried

in vacuo then redissolved in toluene and flashed through silica gel Removal of the

volatiles in vacuo afforded analytically pure material (87 mg 84) 1H NMR (C6D6 300

MHz) δ 938ndash935 (m 2H) 771ndash768 (m 2H) 728ndash722 (m 4H) 670ndash668 (m 2H)

646ndash641 (m 2H) 079 (t J = 30 Hz 18H) 13C1H NMR (C6D6 75 MHz) δ 15259

(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119

Hz) 31P1H NMR (C6D6 121 MHz) δ ndash296 Anal Calcd For C24H30IN3P2Ru C

4432 H 465 N 646 Found C 4432 H 470 N 648

Synthesis of trans-(BQA)RuH(PMe3)2 (614) To a green solution of 611 (37

mg 0066 mmol) in toluene (5 mL) was added 68 microL of a 025 M solution of LiAlH4 in

THF at room temperature The mixture was stirred at room temperature for 5 h after

which the volatiles were removed in vacuo The residue was extracted into toluene and

filtered through a Celite pad The volatiles were removed in vacuo and the solid obtained

was triturated with petroleum ether to give an analytically pure black green solid (26 mg

75) Scaling the reaction up resulted in drastically diminished yields 1H NMR (C6D6

300 MHz) δ 844 (br s 2H) 787ndash784 (m 2H) 739ndash728 (m 4H) 675ndash672 (m 2H)

637ndash633 (m 2H) 080 (br s 18H) ndash1175 (t 2JP-H = 274 Hz) 31P1H NMR (C6D6

121 MHz) δ 147 IR (Nujol mullKBr) υRu-H 17430 cmndash1 Anal Calcd For

C24H31N3P2Ru C 5495 H 596 N 801 Found C 5499 H 588 N 796

Synthesis of trans-(BQA)RuMe(PMe3)2 (615) A green solution of 611 (010 g

019 mmol) in toluene (5 mL) was treated with 35 equivalents of MeLi (10 M) in diethyl

ether at ndash 30 ordmC The mixture was then heated at 60 ordmC for 12 h The reaction mixture

was cooled to room temperature and the excess MeLi was quenched with ethanol The

198volatiles were then removed in vacuo The resulting residue was extracted with benzene

and filtered through a pad of Celite The filtrate was concentrated in vacuo triturated

with petroleum ether and dried in vacuo to yield a green solid (51 mg 50) 1H NMR

(C6D6 300 MHz) δ 828ndash826 (m 2H) 784ndash781 (m 2H) 737ndash730 (m 4H) 675ndash672

(m 2H) 647ndash642 (m 2H) 057 (t J = 27 Hz 18H P(CH3)3) 001 (t J = 98 Hz 3H

RuCH3) 31P1H NMR (C6D6 121 MHz) δ 318 Anal Calcd C25H33N3P2Ru C 5575

H 618 N 780 Found C 5536 H 600 N 778

Synthesis of trans-(BQA)RuN3(PMe3)2 (616) A green solution of 611 (010 g

019 mmol) in CH2Cl2 was treated with solid sodium azide (48 mg 070 mmol) The

mixture was stirred at 50 ordmC for 4h The volatiles were then removed in vacuo The

resulting residue was extracted with benzene and filtered through a pad of Celite The

filtrate was concentrated in vacuo triturated with petroleum ether and dried in vacuo to

yield a green solid (64 mg 64) 1H NMR (C6D6 300 MHz) δ 878ndash875 (m 2H) 766ndash

763 (m 2H) 731ndash720 (m 4H) 672ndash669 (m 2H) 659ndash654 (m 2H) 056 (t J = 30

Hz 18H) 31P1H NMR (C6D6 121 MHz) δ 166 IR (NujolKBr) υN3 = 20281 cmndash1

Anal Calcd For C24H30N6P2Ru C 5097 H 535 N 1486 Found C 5114 H 523 N

1440

Synthesis of Synthesis of 35-(CF3)2Ph-QAH (617) A 200 mL reaction vessel

equipped with a Teflon stopcock and stir bar was charged with Pd2(dba)3 (0218 g 0238

mmol) 11acute-bis(diphenylphosphino)ferrocene (DPPF) (0264 g 0476 mmol) and

toluene (30 mL) under a dinitrogen atmosphere The resulting solution was allowed to

stir for five minutes after which time 35-bis(triflouromethyl)bromobenzene (349 g 119

mmol) 8-aminoquinoline (248 g 119 mmol) and additional toluene (70 mL) were

199added The subsequent addition of sodium tert-butoxide (160 g 1666 mmol) resulted in

a brown solution that was stirred vigorously for three days at 110degC under vacuum The

solution was then allowed to cool and filtered through a silica plug that was then

extracted with dichloromethane to ensure complete removal of the desired product

Concentration of the collected extracts and removal of solvent yielded a crude red solid

(398 g 94) Purification by flash chromatography on silica gel (41 tolueneethyl

acetate) yielded a burgundy red liquid as a spectroscopically pure and synthetically useful

compound (37 g 873) 1H NMR (C6D6 300 MHz 25degC) δ 850 (dd J = 18 42 Hz

1H) 840 (s 1H) 753 (dd J = 18 84 Hz 1H) 736 (m J = 09 Hz 1H) 728 (s 2H)

723 (dd J = 15 72 Hz 1H) 695-704 (m 2H) 682 (dd J = 42 42 Hz 1H) 13C

NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127

MHz 25degC) δ -634 ES-MS (Electrospray) calcd for C17H10F6N2 (M)+ mz 356 found

(M+H)+ mz 357

Synthesis of 35-(CF3)2Ph-QA[Na]middot(Et2O) (618) A suspension of NaH (60

by weight) (57 mg 14 mmol) in Et2O (2 mL) was added to a solution of 35-(CF3)2Ph-

QAH (500 mg 14 mmol) in Et2O (4 mL) Upon heating to 65degC a red-orange salt

precipitated After 10 hours of heating the reaction was cooled to room temperature and

the solvent decanted away The salt was washed with petroleum ether (4 x 5 mL) and

dried in vacuum to afford an orange powder (544 mg 86) Hydrolysis of the salt with

water cleanly affords the parent amine 1H NMR (C6D6 300 MHz 25degC) δ 758 (dd J =

18 42 Hz 1H) 749 (dd J = 18 84 Hz 1H) 738 (dd J = 12 78 Hz 1H) 718 (t J

= 78 Hz 1H) 712 (s 1H) 708 (s 2H) 684 (dd J = 12 78 Hz 1H) 665 (dd J = 42

20084 Hz 1H) 301 (q (CH3CH2)2O J = 72 Hz 4H) 086 (t (CH3CH2)2O J = 72 Hz 6H)

19F NMR (C6D6 282127 MHz 25degC) δ -65

Synthesis of (BQA)Ru(35-(CF3)2Ph-QA)(PPh3) (619) A solution of 618

(2451 mg 054 mmol) in THF (2 mL) was added dropwise to a stirring solution of 65

(500mg 054 mmol) in THF (4 mL) The reaction solution was heated to 80 ordmC for 3h

The reaction was then cooled to room temperature and the volatiles removed in vacuo

The purple solid was washed with a 31 petroleum ether and ethanol mix (3 x 5 mL) The

remaining solid was dried in vacuo yielding 476 mg of analytically pure material (90)

Crystals were grown by cooling a solution of 619 in benzene layered with petroleum

ether 1H NMR (C6D6 300 MHz 25degC) δ 899 (dd J = 12 48 Hz 1H) 757 (dd J =

12 48 Hz 2H) 749 (dd J = 12 82 Hz 1H) 719 (d J = 12 Hz 1H) 677-708 (m

14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608

(dd J = 48 82 Hz 2H) 31P 1H NMR (C6D6 1214 MHz 25degC) δ 505 19F NMR

(C6D6 282127 MHz 25degC) δ -64 ES-MS (Electrospray) calcd for C53H36F6N5PRu

(M)+ mz 988 found (M+H)+ mz 989 Anal Calcd For C53H36F6N5PRu C 6437 H

367 N 708 Found C 6438 H 364 N 708

Synthesis of (BQA)Ru(35-(CF3)2Ph-QA)(CO) (620) A 100 mL reaction

vessel equipped with a Teflon stopcock and stir bar was charged with a solution of 619

(50 mg 005 mmol) in toluene (15 mL) The reaction vessel was evacuated and then

exposed to 1 atm of CO gas The reaction mixture was heated at reflux with vigorous

stirring for 8 h The reaction was then cooled to room temperature and the volatiles

removed in vacuo The red solid was washed with a 31 petroleum ether and ethanol mix

(3 x 5 mL) The remaining solid was dried in vacuo yielding 36 mg of analytically pure

201material (95) 1H NMR (C6D6 300 MHz 25degC) δ 901 (dd J = 12 48 Hz 1H) 750

(dd J = 12 48 Hz 2H) 748 (dd J = 12 82 Hz 1H) 720 (d J = 12 Hz 1H) 677-

708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s

2H) 608 (dd J = 48 82 Hz 2H) 19F NMR (C6D6 282127 MHz 25degC) δ -64 Anal

Calcd For C36H21F6N5ORu C 5730 H 280 N 928 Found C 5702 H 278 N 918

Synthesis of [(BQA)RuCl(PhBP2)][NEt4] (621) A solution of

[Ph2B(CH2PPh2)2][NEt4] (354 mg 051 mmol) in THF (2 mL) was added dropwise to a

stirring solution of 65 (471mg 051 mmol) in THF (4 mL) The reaction solution was

heated to 80 ordmC for 3h The reaction was then cooled to room temperature and the solvent

removed in vacuo The dark purple solid was washed with Et2O (2 x 15 mL) and

petroleum ether (2 x 15 mL) The remaining solid was dried in vacuo yielding 497 mg of

analytically pure material (89) Crystals of 621 were grown by vapor diffusion of

petroleum ether into THF 1H NMR (C6D6 300 MHz 25degC) δ 846 (bs 4H) 793 (bs

2H) 775 (bs 2H) 749 (d J = 63 Hz 2H) 695-739 (m 18H) 679 (t J = 72 Hz 5H)

667 (t J = 72 Hz 4H) 636-647 (m 9H) 329 (q J = 75 Hz 8H) 235 (bs 2H) 181

(bs 2H) 123 (tt J = 15 72 Hz 12 H) 31P 1H NMR (C6D6 1214 MHz 25degC) δ 54

(d J = 36 Hz) 283 (d J = 36 Hz) 11B 1H NMR (C6D6 1283 MHz 25degC) δ -118

Anal Calcd For C64H66BClN4P2Ru C 6985 H 604 N 509 Found C 6978 H 605

N 508

Synthesis of (BQA)Ru(PhBP2) (622) Solid 621 (1006 mg 009 mmol) was

stirred vigorously in ethanol (6 mL) for 30 minutes A red solid precipitated from

solution and was isolated by decanting the liquor away The solids were dissolved in

CH2Cl2 and filtered through a pad of Celite The solvent was removed in vacuo and the

202remaining wine red solid was washed with petroleum ether (2 x 3 mL) and dried in vacuo

yielding 72 mg of analytically pure material (84) 1H NMR (C6D6 300 MHz 25degC) δ

817 (s 5 H) 772 (d J = 48 Hz 2H) 754 (m 10 H) 730 (d J = 6 Hz 4H) 704 (d J =

87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269

(s 4 H) 31P 1H NMR (C6D6 1214 MHz 25degC) δ 6945 11B 1H NMR (C6D6 1283

MHz 25degC) δ -121 Anal Calcd For C56H46BN3P2Ru C 7195 H 496 N 450

Found C 7178 H 505 N 444

Synthesis of (BQA)Ru(CO)(PhBP2) (623) A 20 mL vial containing 621 (60

mg 0054 mmol) in CH2Cl2 (2 mL) was sparged with CO gas The solution instantly

reddened upon contact with the gas The solvent was removed in vacuo and the

remaining red solid was washed with ethanol (2 x 2 mL) The resulting powder was

washed with petroleum ether (2 x 3 mL) and dried in vacuo yielding 45 mg of

analytically pure material (86) 1H NMR (C6D6 300 MHz 25degC) δ 790 (m 4 H) 775

(d J = 45 Hz 2H) 753 (d J = 72 Hz 2 H) 732 (d J = 81 Hz 2H) 711-722 (m 8H)

704 (t J = 75 Hz 4H) 692 (s 6 H) 667 (t J = 66 Hz 2 H) 653 (d J = 75 Hz 2 H)

627-644 (m 10 H) 278 (d J = 12 Hz 2 H) 202 (d J = 138 Hz 2 H) 13C NMR

(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214

MHz 25degC) δ 3517 (d J = 35 Hz) 1881 (d J = 35 Hz) 11B 1H NMR (C6D6 1283

MHz 25degC) δ -119 IR (CH2Cl2) υCO = 1970 cm-1 Anal Calcd For C57H46BN3OP2Ru

C 7110 H 482 N 436 Found C 7106 H 470 N 428

Synthesis of [trans-(BQA)Ru(CO)(PPh3)2][BPh4] (625) NaBPh4 (182mg 005

mmol) in ethanol (1 mL) was added to a solution of 65 (45mg 005 mmol) in THF (2

203mL) in a 10 mL Sclenk flask equipped with a stir bar and septum The flask was

evacuated then exposed to 1 atm of CO gas The green solution reddens instantly upon

exposure to CO The reaction was allowed to stir for 30 minutes before the volatiles were

removed in vacuo The red solid was washed with ethanol (2 x 3 mL) and Et2O (2 x 3

mL) The remaining solid was dried in vacuo yielding 49 mg of analytically pure material

(82) 1H NMR not diagnostic 31P 1H NMR (C6D6 1214 MHz 25degC) δ 301 IR

(CH2Cl2KBr) υCO = 1970 cm-1 ES-MS (Electrospray) calcd for C55H42N3OP2Ru (M)+

mz 924 found (M)+ mz 924 662 (M-PPh3) Anal Calcd For C79H62BN3OP2Ru C

7632 H 503 N 338 Found C 7615 H 487 N 336

Synthesis of [trans-(BQA)Ru(CH3CN)(PPh3)2][BPh4] (624) A solution of 65

(88 mg 0094 mmol) in a mixture of acetonitrile and methanol (2 mL4 mL) was added

to a solution of NaBPh4 (51 mg 015 mmol) in methanol (2 mL) at room temperature

The resulting mixture was stirred at room temperature for 4 h then the volatiles were

removed in vacuo The solid residue was extracted with dichloromethane (5 mL) and

filtered through a Celite pad The volatiles were removed in vacuo and the purple solid

was triturated with petroleum ether The solids were dried in vacuo to afford 78 mg of

analytically pure material (67) 1H NMR not diagnostic 31P1H NMR (CDCl3 121

MHz) δ 287 (bs) Anal Calcd For C78H62BN3P2Ru C 7709 H 514 N 346 Found C

7748 H 569 N 369

Synthesis of [trans-(BQA)Os(CO)(PPh3)2][PF6] (626) A solution of TlPF6

(136 mg 002 mmol) in THF (1 mL) was added to a solution of 66 (40 mg 002 mmol)

in THF (2 mL) in a 10 mL Sclenk flask equipped with a stir bar and septum The flask

was evacuated then exposed to 1 atm of CO gas The green solution reddens after stirring

204vigorously over the period of 1 h The reaction was allowed to stir for 5 h and then the

volatiles were removed in vacuo The red solid was washed with ethanol (2 x 3 mL) and

Et2O (2 x 3 mL) The remaining solid was dried in vacuo yielding 48 mg of analytically

pure material (90) 1H NMR not diagnostic 31P 1H NMR (C6D6 1214 MHz 25degC) δ

031 IR (CH2Cl2KBr) υCO = 1921 cm-1 ES-MS (Electrospray) calcd for

C55H42N3OOsP2 (M)+ mz 1013 found (M)+ mz 1014 Anal Calcd For

C55H42F6N3OOsP3 C 5704 H 366 N 363 Found C 5664 H 351 N 360

Synthesis of [trans-(BQA)RuCl(PPh3)2][OTf] (627) To a vigorously stirring

solution of 65 (011 g 012 mmol) in toluene (5 mL) was added solid AgOTf (30 mg

012 mmol) at room temperature The reaction mixture turned brown instantly while a

black precipitate formed After the mixture was stirred for 1 h the solution was filtered

through a Celite pad to remove the precipitate The volatiles were removed in vacuo The

solids were then extracted into CH2Cl2 (5 mL) and filtered again through a Celite pad

The volume of the filtrate was reduced to 1 mL layered with diethyl ether and allowed

to stand A yellow precipitate formed and was isolated by decanting the liquor The solids

were dried in vacuo to afford analytically pure material (012 g 93) ES-MS

(Electrospray) calcd for C54H42ClN3P2Ru (M)+ mz 931 found (M+H)+ mz 931 Anal

Calcd For C55H42ClF3N3O3P2RuS C 6114 H 392 N 389 Found C 6081 H 370

N 376

Synthesis of [trans-(BQA)Ru(N2)(PPh3)2][PF6] (630) TlPF6 (188 mg 0054

mmol) in THF (1 mL) was added to a solution of 65 (50 mg 0054 mmol) in THF (2

mL) at room temperature The green solution darkens to a midnight blue after stirring for

several hours and the evolution of a white precipitate is noticeable The reaction mixture

205was allowed to stir for 24 h filtered through a Celite pad and then the volatiles were

removed in vacuo Dissolution the blue solids in CH2Cl2 caused the color to change to an

intense red The solution was filtered through a Celite pad and the volatiles were removed

in vacuo The red solid was washed with Et2O (2 x 3 mL) The remaining solid was dried

in vacuo yielding 56 mg of analytically pure material (83) 1H NMR (CD2Cl2 300

MHz 25degC) δ 864-704 (m 42H) 31P 1H NMR (CD2Cl2 1214 MHz 25degC) δ 25 -

143 (sept J = 711 Hz) ES-MS (Electrospray) calcd for C54H42ClN5P2Ru (M)+ mz 924

found (M+H)+ mz 896 (M-N2)+ IR (CH2Cl2KBr) υNN = 2130 cm-1 Anal Calcd For

C54H42F6N5P3Ru C 6068 H 396 N 655 Found C 6055 H 390 N 648

Synthesis of [trans-(BQA)Ru(N2)(PMe3)2][PF6] (631) TlPF6 (188 mg 0054


mL) at room temperature The green solution reddens after stirring for several hours and

the evolution of a white precipitate is noticeable The reaction mixture was allowed to stir

for 36 h filtered through a Celite pad and then the volatiles were removed in vacuo The

solids were dissolved in CH2Cl2 filtered through a Celite pad and the volatiles were

removed in vacuo The red solid was washed with Et2O (2 x 3 mL) The remaining solid

was dried in vacuo yielding 36 mg of analytically pure material (78) 1H NMR (CD2Cl2

300 MHz 25degC) δ 835 (d J = 51Hz 2H) 804 (d J = 78 Hz 2H) 791 (d J = 78 Hz

2H) 754 (t J = 78 Hz 2H) 725 (dd J = 78 78 Hz 2H) 704 (d J = 78 Hz 2H) 072

(t J = 27Hz 9H) 31P 1H NMR (CD2Cl2 1214 MHz 25degC) δ 042 -143 (sept J = 711

Hz) ES-MS (Electrospray) calcd for C24H30N5P2Ru (M)+ mz 552 found (M+H)+ mz

524 (M-N2)+ IR (CH2Cl2KBr) υNN = 2129 cm-1 Anal Calcd For C24H30F6N5P3Ru C

4139 H 434 N 1005 Found C 4129 H 415 N 989

206 Synthesis of [trans-(BQA)Os(N2)(PPh3)2][PF6] (632) A solution of TlPF6 (136

mg 002 mmol) in THF (1 mL) was added to a solution of 66 (40 mg 002 mmol) in

THF (2 mL) at room temperature The green solution reddens after stirring vigorously

over the period of several hours The reaction was allowed to stir for 24 h filtered

through a Celite pad and then the volatiles were removed in vacuo The red solid was

extracted into CH2Cl2 and filtered through a Celite pad The volatiles were removed in

vacuo and the resultant solids were washed with Et2O (2 x 3 mL) The remaining solid

was dried in vacuo yielding 48 mg of analytically pure material (89) 1H NMR not

diagnostic 31P 1H NMR (C6D6 1214 MHz 25degC) δ -37 IR (CH2Cl2KBr) υNN =

2073 cm-1 ES-MS (Electrospray) calcd for C54H42N5OsP2 (M)+ mz 1013 found (M)+

mz 1014 986 (M-N2)+ Anal Calcd For C54H42F6N5OsP3 C 5600 H 366 N 605

Found C 5592 H 361 N 599

207References Cited 1 Allen A D Senoff C V J Chem Soc Chem Comm 1965 621

2 See Laplaza C E Johnson M J A Peters J C Odom A L Kim E Cummins

C C George G N Pickering I J J Am Chem Soc 1996 118 8623 and references

7-9 therein

3 MacKay B A Fryzuk M D Chem Rev 2004 104 385

4 Laplaza C E Cummins C C Science 1995 268 861

5 (a) Antipin M Struchkov Y Shilov A Shilova A Gass Chim Ital 1993 123

265 (b) Luneva N P Mironova S A Shilov A E Antipin M Y Struchkov Y T

Angew Chem Int Ed Eng 1993 32 1178 (c) Shilov A E Pure Appl Chem 1992

64 1409 (d) Yandulov D V Schrock R R Science 2003 301 76

6 Fryzuk M D Love J B Rettig S J Young V G Science 1997 275 1445

7 Fryzuk M D MacKay B A Johnson S A Patrick B O Angew Chem Int Ed

2002 41 3709

8 Fryzuk M D MacKay B A Patrick B O J Am Chem Soc 2003 125 3234

9 Chatt J Dilworth R L Chem Rev 1978 78 589

10 (a) Hidai M Mizobe Y Chem Rev 1995 95 1115 (b) Nishibayshi Y Iwai S

Hidai M Science 1998 279 540 (c) Hidai M Coord Chem Rev 1999 185 99

11 (a) Collman J P Braumann J I Fitzgerald J P Sparapany J W Ibers J A J

Am Chem Soc 1988 110 3486 (b) Collman J P Hutchison J E Lopez M A

Guilard R Reed R A J Am Chem Soc 1991 113 2794 (c) Collman J P

Hutchison J E Lopez M A Guilard R J Am Chem Soc 1992 114 8066 (d)

Collman J P Hutchison J E Ennis M S Lopez M A Guilard R J Am Chem

208 Soc 1992 114 8074 (e) Collman J P Wagenknecht P S Hutchison J E Angew

Chem Int Ed Engl 1994 33 1537

12 (a) Buhr J D Taube H Inorg Chem 1979 18 2208 (b) Ware D C Taube H

Inorg Chem 1991 30 4598 (c) Ware D C Taube H Inorg Chem 1991 30 4605

13 Pipes D W Bakir M Vitols S E Hodgson D J Meyer T J J Am Chem Soc

1990 112 5507

14 For representative examples of recent ldquopincer-ligandrdquo chemistry see (a) van der

Boom M E Milstein D Chem Rev 2003 103 1759 (b) Albrecht M Spek A L

van Koten G J Am Chem Soc 2001 123 7233 (c) Rodriguez G Albrecht M

Schoenmaker J Ford A Lutz M Spek A L van Koten G J Am Chem Soc 2002

124 5127 (d) Krogh-Jespersen K Czerw M Summa N Renkema K B Achord P

D Goldman A S J Am Chem Soc 2002 124 11404 (e) Zhao J Goldman A S

Hartwig J F Science 2005 307 1080 (f) Fryzuk M D MacNeil P A Rettig S J

Secco A S Trotter J Organometallics 1982 1 918 (g) Fryzuk M D Leznoff D B

Thompson R C Rettig S J J Am Chem Soc 1998 120 10126 (h) Deacon G B

Gatehouse B M Grayson I L Nesbit M C Polyhedron 1984 3 753 (i) Buxton D

P Deacon G B Gatehouse B M Grayson I L Wright P J Acta Crystallogr Sect

C 1985 41 1049 (j) Dori Z Eisenberg R Steifel E I Gray H B J Am Chem Soc

1970 92 1506 (k) Kawamoto T Nagasawa I Kuma H Kushi Y Inorg Chim Acta

1997 265 163 (l) Endres H Keller J Poveda A Z Naturforsch B 1977 32 131 (h)

Sacco A Vasapollo G Nobile C F Piergiovanni A Pellinghelli M A Lanfranchi

M J Organomet Chem 1988 356 397

15 Peters J C Harkins S B Brown S D Inorg Chem 2001 40 5083

209 16 (a) Sur S K J Magn Reson 1989 82 169 (b) Evans D F J Chem Soc 1959

2003

17 Maiti D Paul H Chanda N Chakraborty S Mondal B Puranik V G Lahiri

G K Polyhedron 2004 831

18 Connelly N G Geiger W E Chem Rev 1996 96 877

19 Sauvage J-P Collin J-P Chambron J-C Guillerez S Coudret C Balzani V

Barigelletti F De Cola L Flamigni L Chem Rev 1994 94 993

20 Sullivan B P Calvert J M Meyer T J Inorg Chem 1980 19 1404

21 (a) Vila J M Pereira M T Ortigueira J M Lata D Lopez Torres M

Fernandez J J Fernandez A Adams H J Organomet Chem 1998 566 93 (b)

Crespo M Solans X Font-Bardia M Polyhedron 1998 17 3927 (c) Gandelman

Vigalok A Shimon L J W Milstein D Organometallics 1997 16 3981

22 Thomas J C Peters J C J Am Chem Soc 2001 123 5100

23 Tenorio M A J Tenorio M J Puerta M C Valerga P J Chem Soc Dalton

Trans 1998 3601

24 Karlen T Dani P Grove D M Steenwinkel P van Koten G Organometallics

1996 15 5687

25 Stoicheff B P Can J Phys 1954 82 630

26 Hallman P S Stephenson T A Wilkinson G Inorg Synth 1970 12 237

27 Bennett M A Smith A K J Chem Soc Dalton Trans 1974 233

28 Elliott G P McAuley N M Roper W R Inorg Synth 1989 26 184

162

Abstract

Entry into the group VIII chemistry of the bis(8-quinolinyl)amine (BQA 61)

ligand was effected by both protolytic and metathetical strategies The bis-ligated Fe(III)

complex [Fe(BQA)2][BPh4] (62) was prepared via amine addition to FeCl3 in the

presence of base and NaBPh4 The cation 62 is low-spin (S = frac12) and exhibits a rhombic

EPR signal (4 K X-band) Complexes featuring a single BQA ligand were prepared for

Ru and Os Reaction of the polymeric [RuCl2(cod)]n species with one equivalent of

LiBQA afforded the divalent complex (BQA)RuCl(cod) (63) while two equivalents of

LiBQA afforded the neutral congener of 62 Ru(BQA)2 (64) (cod = 14-cycloocatdiene)

Reaction of LiBQA with the phosphine containing precursors (PPh3)3MCl2 exclusively

afforded the trans-(BQA)MCl(PPh3)2 complexes (M = Ru 65 Os 66) Reaction of

HBQA with (PPh3)3MCl2 and external base (NEt3) afforded 65 for M = Ru but afforded

the isomer of 66 cis-(BQA)OsCl(PPh3)2 (67) for M = Os Complexes 63 65 and 66

were crystallographically characterized in the solid-state by X-ray diffraction Complexes

62 65 and 66 were examined for the electrochemical behavior and displayed well-

defined reversible MIIIII redox events All three species exhibit a second reversible redox

event that may be attributable to a reversible oxidation of the BQA ligand Complex 64

was compared electrochemically against the dication [(tpy)2Ru]2+ and the monocation

[(tpy)Ru(BQA)]+ (69) The RuIIIII redox couple shifts -06 V from the dication to the

monocation 69 and an additional -05 V from 69 to the neutral complex 64 Phosphine

exchange from 65 provided (BQA)RuCl(PEt3)2 (610) and (BQA)RuCl(PMe3)2 (611)

preserving the trans arrangement of the phosphine ligands Halide substitution of 611

was effected by refluxing in THF with KX salts to yield (BQA)RuBr(PMe3)2 (612) and

















characterized

16461 Introduction

























and Fryzuk (right)









































168Scheme 61


















spin









occupied d orbital




170


from 650-750 nm













in the spectrum

172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





















characterized

16461 Introduction

























and Fryzuk (right)









































168Scheme 61


















spin









occupied d orbital




170


from 650-750 nm













in the spectrum

172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





16461 Introduction

























and Fryzuk (right)









































168Scheme 61


















spin









occupied d orbital




170


from 650-750 nm













in the spectrum

172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687









and Fryzuk (right)









































168Scheme 61


















spin









occupied d orbital




170


from 650-750 nm













in the spectrum

172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687
































168Scheme 61


















spin









occupied d orbital




170


from 650-750 nm













in the spectrum

172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687







spin









occupied d orbital




170


from 650-750 nm













in the spectrum

172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





170


from 650-750 nm













in the spectrum

172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687














in the spectrum

172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





172










173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





173



















174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





174

















175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





175


Scheme 62

































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687































likely

178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





178















displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687






displacement

Scheme 63



























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687

























181Scheme 64
















621 in THF

182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





182









183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





183Scheme 65



















= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687










= 1921 cm-1) from 625

Scheme 66











































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687






































Scheme 67

187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





187





8080(1) N1-Os-N3 1606(1) P1-Os-P2 1774(1)

63 Conclusions



















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687















189





Formula Weight 59311 93036 109860 98891 134243 115804



Z 8 4 4 4 2 4 Dcalcd

(gcm3) 1537 1449 1547 1572 1380 1692


00299 00631 00502 00849 00244 00582 00256 00487 00696 01359 00288 00642


2)2]Σ[w(Fo2)2]12

190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687





190
























diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687






diffractometer












atmosphere























(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687


















(CDCl3 75 MHz) δ 14994 13714 13168 12883 12842 12260 12203 11352



C 6073 H 482 N 789












C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687










C 6763 H 366 N 1312













6963 H 455 N 451 found C 6893 H 469 N 449













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687













6355 H 415 Cl 347 N 412 found C 6346 H 402 N 410












(M-Cl)










475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687












475 N 906



















(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687








(C6D6 75 MHz) δ 15256 15174 14827 (t J = 24 Hz) 13232 (t J = 17 Hz) 13178

12814 12194 (t J = 16 Hz) 11369 11336 1103 (t J = 113 Hz) 31P1H NMR



Found C 5166 H 535 N 743









NMR (C6D6 75 MHz) δ 15202 15152 14972 (t J = 23 Hz) 13242 13168 12812



650









(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687










(m) 15150 15073 13275 13179 12830 12232 11382 11365 1283 (t J = 119


4432 H 465 N 646 Found C 4432 H 470 N 648






















H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687











H 618 N 780 Found C 5536 H 600 N 778










1440

















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687















NMR (C6D6 75409 MHz 25degC) δ 1481 1442 1396 1387 1365 1333 1329

1295 1276 1261 1224 1194 1182 1145 (m) 1101 19F NMR (C6D6 282127


(M+H)+ mz 357











19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687






19F NMR (C6D6 282127 MHz 25degC) δ -65










14H) 675 (m 6H) 658-664 (m 5H) 653 (dd J = 54 72 Hz 1H) 644 (s 2H) 608




367 N 708 Found C 6438 H 364 N 708










708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687







708 (m 14H) 670 (m 6H) 658-664 (m 5H) 652 (dd J = 54 72 Hz 1H) 644 (s
















N 508








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687








87 Hz 2H) 6851 (d J = 78 Hz 2H) 650 (m 10 H) 62 (m 2 H) 581 (m 2 H) 269



Found C 7178 H 505 N 444










(C6D6 75409 MHz 25degC) δ 155 151 149 137 135 1332 1331 1326 1325 131

129 1285 1284 128 127 1268 1267 123 120 114 31P 1H NMR (C6D6 1214



C 7110 H 482 N 436 Found C 7106 H 470 N 428











7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687













7632 H 503 N 338 Found C 7615 H 487 N 336










7748 H 569 N 369























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687























N 376



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687



























4139 H 434 N 1005 Found C 4129 H 415 N 989












Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687
















Found C 5592 H 361 N 599




7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687








7-9 therein









2002 41 3709















1990 112 5507



















2003













Trans 1998 3601


1996 15 5687










1990 112 5507



















2003













Trans 1998 3601


1996 15 5687






2003













Trans 1998 3601


1996 15 5687





chapter 6. group viii coordination chemistry supported by ... · group viii coordination chemistry...

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