supporting information - royal society of chemistryair stable nhcs: a study of stereoelectronics and...

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Supporting Information

for

Air Stable NHCs:

A Study of Stereoelectronics and Metallorganic Catalytic Activity

Samantha K. Furfari, Matthew R. Gyton, Daniel Twycross and Marcus L. Cole*

School of Chemistry, University of New South Wales, Sydney,

NSW 2052, Australia

E-mail: [email protected]

Table of Contents

Synthetic procedures………………………………………………………………. S2-S9

IPrBr………. S3

1L………….. S3-S4

2L………….. S5

3L………….. S6-S7

4L………….. S8-S9

Catalyses…………………………………………………………………………… S10-S11

Single crystal X-ray diffraction structure determinations………………………… S12-S16

Steric bulk calculations for 1L determined by the program Solid-G.……………… S17-S40

XPS data for 1L ………….………………………………………………………… S41-S42

References………………………………………………………………………….. S43

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2014

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Synthetic procedures

All synthetic manipulations were performed using standard Schlenk and glove box

techniques under an atmosphere of ultra high purity (UHP) or high purity argon, unless

otherwise specified. All organic solvents were dried, degassed and stored for use under argon

in J. Young valved ampoules. Diethyl ether, hexane, tetrahydrofuran and toluene were

distilled from sodium benzophenone ketyl. Dichloromethane and pentane were collected

from an Innovative Technology MD-7 solvent purification system. The latter was stored over

a potassium mirror. Isopropyl alcohol was distilled from calcium hydride.

Imidazolium chloride NHC precursors were synthesised using the procedure of

Hintermann.[S1]

The free NHCs IMes and IPr were prepared by treatment of the imidazolium

salt with one equivalent of nbutyllithium (

nBuLi) or potassium tert-butoxide (KO

tBu) in

tetrahydrofuran followed by recrystallisation from diethyl ether (IMes) or toluene (IPr).

nButyllithium solutions in hexane were decanted into J. Youngs tapped flasks under UHP

argon and standardised with N-benzyl benzamide in accordance with the method of

Chong.[S2]

IMesBr was prepared using a modified literature procedure whereby toluene was

used as reaction solvent.[S3]

The metal complexes [{Ir(µ-Cl)(cod)}2],[S4]

[{PdBr(µ-

Br)(iPrBzim)}2],

[S5] [{Pd(µ-Cl)(η

3-Cin)}2],

[S6][S7] 1

IMes,[S8]

1IPr[S8]

and 4IPr[S7]

were synthesised

according to literature procedures. Carbon tetrabromide was acquired from Alfa-Aesar and

sublimed prior to use. All other reagents and gases were purchased from Alfa-Aesar, Ajax

Fine chemicals, Precious Metals Online, Sigma-Aldrich, BOC or Strem and used as received.

1H and

13C NMR spectra were recorded on a Bruker DPX 300, Bruker Avance III 300 (

1H:

300.13 MHz and 13

C: 75.45 MHz), Bruker DPX 400, Bruker Avance III 400 (1H: 400.13

MHz and 13

C: 100.62 MHz) or a Bruker Avance III 500 (1H: 500.13 MHz and

13C: 125.76

MHz) spectrometer at 298 K. HMBC correlation experiments were conducted using a Bruker

Avance III 400 (1H: 400.13 MHz and

13C: 100.62 MHz) and, due to signal overlap in the

1H

NMR aromatic region, referenced to the methylene resonances of residual dichloromethane in

CDCl3.

All spectra were recorded as solutions in deuterobenzene (C6D6) or

deuterochloroform (CDCl3) and referenced to the resonances of residual non-deuterated

solvent according to the data of Fulmer.[S9]

Deuterobenzene was stored over sodium and

freeze-thaw degassed prior to use. Multiplicities are denoted as singlet (s), doublet (d), septet

(sept) or multiplet (m) and prefixed broad (br) where applicable. 13

C NMR spectra for 3IMesBr

and 3IPrBr

were collected using near saturated solutions with analytically pure samples.

Compounds for infrared spectroscopy (4000 to 400 cm-1

) were prepared as Nujol mulls or

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dichloromethane solutions and the spectra recorded on a Nicolet Avatar 320 FTIR

spectrophotometer (NaCl windows). Spectra are reported in wavenumbers (cm-1

) and the

intensity of the absorbances is denoted as strong (s), medium (m) or weak (w) and prefixed

broad (br) or sharp (sh) where applicable. Melting points were determined in sealed glass

capillaries under argon and are uncorrected. Microanalyses were conducted at the Campbell

Microanalytical Laboratory at the University of Otago, Dunedin, New Zealand.

IPrBr∙C7H8

A solution of carbon tetrabromide (2.56 g, 7.72 mmol) in toluene (20 cm3) was added

dropwise to a stirred solution of IPr (1.50 g, 3.86 mmol) in toluene (80 cm3) at room

temperature with a slight darkening of the reaction mixture (colourless > light red-brown).

The reaction mixture was stirred for 2 hours at room temperature. Filtration, concentration (to

approximately 5 cm3) and cooling to -15 °C afforded IPrBr as solvent inclusive colourless

prisms suitable for X-ray diffraction structure determination (1.65 g, 2.58 mmol, 67%), dec.

102 °C. 1H NMR (400.13 MHz, C6D6, vacuum dried sample) δ 1.30 (d,

3JHH = 6.8 Hz, 12H,

CH(CH3)2), 1.34 (d, 3JHH = 6.8 Hz, 12H, CH(CH3)2), 2.96 (sept,

3JHH = 6.8 Hz, 4H,

CH(CH3)2), 7.35 (m, 6H, ArH). 13

C NMR (100.62 MHz, C6D6, vacuum dried sample) δ 22.69

(s, CH(CH3)2), 24.56 (s, CH(CH3)2), 28.81 (s, CH(CH3)2), 107.56 (s, NCBr), 123.59 (s, p-

ArCH), 129.64 (s, o-ArC), 139.13 (s, m-ArCH), 146.36 (s, ipso-ArC), 222.36 (s, NCN). IR

(Nujol) ν/cm-1

651.00 (sh s), 684.14 (sh m), 756.74 (sh s), 886.50 (w), 936.73 (sh m), 958.99

(sh s), 1145.75 (m), 1180.00 (m), 1330.30 (br s), 1516.45 (w), 1555.04 (sh m). Anal. Calc. for

C27H34Br2N2: C, 59.35; H, 6.27; N, 5.13. Found (vacuum dried sample): C, 59.32; H, 6.52, N,

5.02 %.

[IrCl(cod)(IPrBr)]∙2C7H8 (1IPrBr

∙2C7H8)

A solution of IPrBr (490 mg, 897 μmol) in toluene (10 cm3) was added dropwise to a stirred

solution of [{Ir(µ-Cl)(cod)}2] (304 mg, 453 μmol) also in toluene (30 cm3) at room

temperature. The reaction mixture was left to stir overnight resulting in a yellow-orange

solution. The solvent was concentrated and placed in a freezer at -15 °C for 48 hours to

afford the title compound as a solvent inclusive dark yellow prisms suitable for X-ray

diffraction structure determination (409 mg, 464 μmol, 52 %), dec. 192 °C. 1H NMR (400.13

MHz, C6D6, vacuum dried sample) δ 1.23-1.32 (m, 28H, CH(CH3)2 & CH2cod), 1.66 (m, 4H,

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CH2cod), 2.18 (br sept, 2H, CH(CH3)2), 3.02 (br sept, 2H, CH(CH3)2), 3.15 (m, 2H, =CHcod),

4.78 (m, 2H, =CHcod), 7.26 (m, 6H, ArH). 1H NMR (500.13 MHz,CDCl3, vacuum dried

sample) δ 1.16-1.45 (br m, 32H, CH(CH3)2 & CH2cod), 2.45 (br m, 2H, CH(CH3)2), 2.97 (m,

2H, =CHcod), 3.60 (v br s, 2H, CH(CH3)2), 4.29 (m, 2H, =CHcod), 7.53 (m, 6H, ArH). 13

C

NMR (100.62 MHz, C6D6, vacuum dried sample) δ 22.89 (s, CH(CH3)2), 23.70 (s,

CH(CH3)2), 28.75 (s, CH(CH3)2), 29.29 (s, CH2cod), 33.62 (s, CH2cod), 50.89 (s, =CHcod),

83.93 (s, =CHcod), 111.00 (s, NCBr), 123.84 (s, p-ArCH), 130.41 (s, o-ArC), 134.61 (s, m-

ArCH), 148.08 (s, ipso-ArC), 191.35 (s, NCN). IR (Nujol) ν/cm-1

665.54 (m), 698.55 (s),

756.49 (s), 800.62 (m), 879.34 (w), 922.52 (br m), 997.62 (m), 1055.71 (br m), 1074.70 (m),

1099.44 (br w), 1230.18 (s), 1287.48 (m), 1365.78 (s), 1567.45 (m), 1601.19 (m). Anal. Calc.

for C35H46Br2ClIrN2∙2C7H8: C, 55.18; H, 5.86; N, 2.63. Found: C, 54.70; H, 6.10; N, 2.88 %.

[IrCl(cod)(IMesBr)] (1IMesBr

)

A solution of IMesBr (373 mg, 807 μmol) in toluene (20 cm3) was added dropwise over 5

mins to a stirred solution of [{Ir(µ-Cl)(cod)}2] (283 mg, 421 μmol) in toluene (20 cm3). The

resulting dark brown solution was stirred overnight and then reduced in volume (~ 20 cm3) to

induce precipitation. Filtration and drying of the filtrant in vacuo gave crude 1IMesBr

as a

bright yellow powder. Recrystallisation from a saturated toluene solution at ambient

temperature afforded yellow prisms of 1IMesBr

suitable for X-ray diffraction structure

determination (446 mg, 559 μmol, 69 %), dec. 229 °C. 1H NMR (400.13 MHz, C6D6) δ 1.32

(m, 4 H, CH2cod), 1.70 (m, 4 H, CH2cod), 1.99 (s, 6H, o- or p-CH3), 2.09 (s, 6H, o- or p-CH3),

2.62 (s, 6H, o- or p-CH3), 3.20 (m, 2H, =CHcod), 4.70 (m, 2H, =CHcod), 6.77 (s, 2H, m-ArH),

6.78 (s, 2H, m-ArH). 1H NMR (300.13 MHz, CDCl3) δ 1.19-1.39 (m, 4H, CH2cod), 1.48-1.71

(m, 4H, CH2cod), 2.08 (s, 6H, o- or p-CH3), 2.34 (s, 6H, o- or p-CH3), 2.38 (s, 6H, o- or p-

CH3), 3.00 (m, 2H, =CHcod), 4.16 (m, 2H, =CHcod), 7.00 (s, 2H, m-ArH), 7.04 (s, 2H, m-

ArH). 13

C NMR (100.62 MHz, C6D6) δ 18.14 (s, o- or p-CH3), 19.85 (s, o- or p-CH3), 20.71

(s, o- or p-CH3), 28.84 (s, CH2cod), 33.61 (s, CH2cod), 50.94 (s, =CHcod), 84.15 (s, =CHcod),

108.84 (s, NCBr), 130.10, 134.58, 134.84, 138.28, 139.24 (s, ArC), 186.32 (s, NCN). IR

(Nujol) ν/cm-1

665.33 (sh w), 724.98 (br w), 802.59 (br w), 851.13 (sh w), 973.19 (sh w),

1030.57 (br w), 1094.99 (br w), 1151.17 (sh w), 1227.67 (sh w), 1261.38 (sh w), 1292.45 (sh

m), 1345.67 (sh m), 1567.82 (sh w), 1608.40 (sh w). Anal. Calc. for C29H34Br2ClIrN2: C,

43.64; H, 4.29; N, 3.51. Found: C, 43.60; H, 4.40; N, 3.31 %.

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cis-[IrCl(CO)2(IPrBr)] (2IPrBr

)

A solution of [IrCl(cod)(IPrBr)] (vacuum dried sample, 298.1 mg, 337.9 μmol) in

dichloromethane (20 cm3) was freeze-thaw degassed and placed under an atmosphere of

carbon monoxide. Stirring overnight resulted in a colour change from yellow to green to dark

brown. Filtration, removal of reaction volatiles in vacuo and washing with pentane (2 x 5

cm3) yielded microcrystalline yellow-orange cis-[IrCl(CO)2(IPrBr)] (185 mg, 223 μmol, 75

%), dec. 203 °C. 1H NMR (400.13 MHz, C6D6) δ 1.18 (d,

3JHH = 6.7 Hz, 12H, CH(CH3)2),

1.57 (d, 3JHH = 6.7 Hz, 12H, CH(CH3)2), 3.10 (sept,

3JHH = 6.7 Hz, 4H, CH(CH3)2), 7.21 (m,

6H, ArH). 13

C NMR (100.62 MHz, C6D6) δ 24.36 (s, CH(CH3)2), 24.96 (s, CH(CH3)2), 28.94

(s, CH(CH3)2), 112.27 (s, NCBr), 124.83 (s, p-ArCH), 131.29 (s, o-ArC), 133.54 (s, m-

ArCH), 146.54 (s, ipso-ArC), 169.69 (s, C≡O or NCN), 178.61 (s, C≡O or NCN), 182.62 (s,

C≡O or NCN). IR (Nujol) ν/cm-1

655.52 (m), 721.65 (br w), 760.99 (m), 803.65 (s), 935.21

(w), 1060.24 (w), 1105.11 (w), 1161.39 (w), 1261.93 (m), 1303.81 (m), 1323.02 (m),

1363.74(s), 1559.63 (m), 1706.97 (br w), 1981.51 (sh s), 2063.17 (sh s). IR (CH2Cl2) ν/cm-1

1984.84 (sh m), 2070.91 (sh m). Anal. Calc. for C29H34Br2ClIrN2O2: C, 41.96; H, 4.13; N,

3.37. Found: C, 42.04; H, 4.37; N, 3.22 %.

cis-[IrCl(CO)2(IMesBr)] (2IMesBr

)

A solution of [IrCl(cod)(IMesBr)] (431 mg, 540 μmol) in dichloromethane (10 cm3) was

freeze-thaw degassed and placed under an atmosphere of carbon monoxide. Stirring for one

hour gave a pale yellow solution. Volatiles were removed in vacuo and the resulting solid

washed with cold pentane (2 x 5 cm3) to afford cis-[IrCl(CO)2(IMesBr)] as a tan-yellow

powder (400 mg, 536 μmol, 99 %), dec. 310 °C. 1H NMR (400.13 MHz, C6D6) δ 1.99 (s, 6H,

p-CH3), 2.24 (s, 12H, o-CH3), 6.79 (s, 4H, m-ArH). 13

C NMR (100.62 MHz, C6D6) δ 18.68

(s, CH3), 21.07 (s, CH3), 110.21 (s, NCBr), 129.87 (s, p-ArCH), 133.89 (s, o-ArC), 135.94 (s,

m-ArCH), 140.59 (s, ipso-ArC), 169.72 (s, C≡O or NCN), 179.56 (s, C≡O or NCN), 179.82

(s, C≡O or NCN). IR (Nujol) ν/cm-1

665.35 (w), 722.55 (w), 800.63 (w), 855.25 (w), 1030.60

(m), 1261.05 (m), 1315.47 (w), 1557.59 (w), 1606.00 (w), 1969.46 (sh s), 2063.51 (sh s). IR

(CH2Cl2) ν/cm-1

1983.18 (sh s), 2069.42 (sh s). Anal. Calc. for C23H22Br2ClIrN2O2: C, 37.04;

H, 2.97; N, 3.76. Found: C, 37.31; H, 3.18; N, 3.50 %.

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General preparation for trans-[PdBr2(iPrBzim)(NHC)] (3

L) complexes

A solution of NHC (2.0 eq.) in dichloromethane (45 cm3 per mmol

of reagent) was added

drop wise to a stirred solution of [{PdBr(µ-Br)(iPrBzim)}2] (1.0 eq.) in THF (90 cm

3 per

mmol of reagent) at ambient temperature followed by stirring overnight. This resulted in a

gradual colour change from brown to light tan. Filtration through a pad of celite (pad washed

with 30 cm3 dichloromethane mmol

-1 of NHC) and concentration in vacuo yielded trans-

[PdBr2(iPrBzim)(NHC)] after standing at 0 °C (NHC = IMesBr) or ambient temperature

(NHC = IPrBr) for several days.

trans-[PdBr2(iPrBzim)(IPrBr)]∙1.5CH2Cl2 (3

IPrBr∙1.5CH2Cl2)

IPrBr (175mg, 320 μmol) and [{PdBr(µ-Br)(iPrBzim)}2] (150 mg, 160 μmol) afforded the

title compound as solvent inclusive pale yellow rectangular plates (151 mg, 105 μmol, 33 %),

m.p. 230 °C (dec. 285 °C). 1H NMR (300.13 MHz, CDCl3, vacuum dried sample) δ 1.23 (d,

3JHH = 6.7 Hz, 12 H, CH(CH3)2, IPrBr), 1.35 (d,

3JHH = 7.0 Hz, 12H, CH(CH3)2,

iPrBzim),

1.46 (d, 3JHH = 6.7 Hz, 12H, CH(CH3)2, IPrBr), 3.06 (sept,

3JHH = 6.7 Hz, 4H, CH(CH3)2,

IPrBr), 5.28 (sept, 3JHH = 7.0 Hz, 2H, CH(CH3)2,

iPrBzim), 7.03 (dd,

AA’XX’JHH = 6.1, 3.1 Hz,

2H, ArH, iPrBzim), 7.33 (dd,

3JHH = 6.1, 3.1 Hz, 2H, ArH,

iPrBzim), 7.42 (d,

AB2JHH = 7.7

Hz, 4H, m-ArH, IPrBr), 7.51 (d, AB2

JHH = 7.7 Hz, 2H, p-ArH, IPrBr). 13

C NMR (75.45 MHz,

CDCl3, vacuum dried sample) δ 21.12 (s, CH(CH3)2, iPrBzim), 25.99 (s, CH(CH3)2, IPrBr),

26.33 (s, CH(CH3)2, IPrBr), 29.51 (s, CH(CH3)2, IPrBr), 54.10 (s, CH(CH3)2, iPrBzim),

111.95 (s, NCBr, IPrBr), 112.85 (s, NCCN, iPrBzim), 122.12 (s, ArCH,

iPrBzim), 125.17 (s,

p-ArCH, IPrBr), 131.05 (s, ArCH, iPrBzim), 134.07 (s, o-ArC, IPrBr), 135.14 (s, m-ArCH,

-

IPrBr), 148.37 (s, ipso-ArC, IPrBr), 174.72 (s, NCN, iPrBzim), 184.65 (s, NCN, IPrBr). IR

(Nujol) ν/cm-1

665.30 (m), 709.42 (w), 744.97 (s), 773.66 (w), 802.39 (s), 845.21 (w), 885.50

(w), 933.04 (w), 956.20 (w), 1022.15 (w), 1059.45 (w), 1093.10 (s), 1108.98 (m), 1140.36 (s),

1174.94 (m), 1239.18 (w), 1264.16 (m), 1300.11 (m), 1314.43 (m), 1362.23 (s), 1404.28 (s),

1423.30 (s), 1554.61 (m), 1589.48 (m), 1705.20 (w). Anal. Calc. for

C40H52Br4N4Pd·1.5CH2Cl2: C, 43.64; H, 4.85; N, 4.90. Found: C, 43.70; H, 5.00; N, 4.77 %

(partial inclusion of lattice solvent).

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trans-[PdBr2(iPrBzim)(IMesBr)]∙CH2Cl2 (3

IMesBr∙CH2Cl2)

IMesBr (148 mg, 320 μmol) and [{PdBr(µ-Br)(iPrBzim)}2] (150 mg, 160 μmol) yielded the

title compound as solvent inclusive light yellow truncated octahedra (137 mg, 135 μmol, 42

%), dec. 273 °C. 1H NMR (400.13 MHz, CDCl3, vacuum dried sample) δ 1.40 (d,

3JHH = 6.9

Hz, 12 H, CH(CH3)2), 2.37 (s, 12H, o-CH3), 2.44 (s, 6H, p-CH3), 5.22 (sept, 3JHH = 6.9 Hz,

2H, CH(CH3)2), 7.07 (m, 6H, ArH, iPrBzim and IMesBr), 7.35 (dd,

AA’XX’JHH = 6.1, 3.0 Hz,

2H, ArH, iPrBzim).

13C NMR (100.62 MHz, CDCl3, vacuum dried sample) δ 20.42 (s,

CH(CH3)2), 21.23 (s, o-CH3), 21.88 (s, p-CH3) 53.85 (s, CH(CH3)2), 109.32 (s, NCBr),

112.66 (s, NCCN, iPrBzim), 122.24 (s, ArCH,

iPrBzim), 129.47 (s, ArCH,

iPrBzim), 134.23

(s, p-ArC, IMesBr), 134.80 (s, o-ArC, IMesBr), 137.99 (s, m-ArCH, IMesBr), 140.00 (s,

ipso-ArC, IMesBr), 175.01 (s, NCN, iPrBzim), 180.43 (s, NCN, IMesBr). IR (Nujol) ν/cm

-1

665.31 (m), 685.67 (w), 731.69 (br s) 807.34 (s), 855.75 (s), 888.29 (w), 914.95 (s), 983.23

(w), 1019.88 (s), 1092.84 (s), 1141.51 (s), 1172.84 (m), 1193.74 (m), 1260.50 (s), 1311.99

(s), 1404.24 (w), 1521.86 (w), 1552.24 (m), 1606.07 (s). Anal. Calc. for

C34H40Br4N2Pd·CH2Cl2: C, 41.39; H, 4.17; N, 5.52. Found: C, 41.66; H, 4.16; N, 5.58 %.

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General preparation for [PdCl(η3-Cinnamyl)(NHC)] complexes

A solution of NHC (2.0 eq.) in THF (15 cm3 mmol

-1) was added drop wise to a stirred

solution of [{Pd(µ-Cl)(η3-Cin)}2] (1.0 eq.) also in THF (20 cm

3 mmol

-1) at ambient

temperature. After stirring for 90 minutes the volatiles were removed in vacuo and

analytically pure 4L isolated by trituration with hexane.

[PdCl(η3-Cin)(IPrBr] (4

IPrBr)

IPrBr (1.60 g, 2.93 mmol) and [{Pd(µ-Cl)(η3-Cin)}2] (0.71 g, 1.37 mmol) yielded the title

compound as pale yellow prisms (2.09 g, 2.59 mmol, 95%), dec. 158 °C. 1H NMR (300.13

MHz, C6D6) δ 1.16 (d, 3JHH 6.8 Hz, 12H, CH(CH3)2), 1.44 (d,

3JHH = 6.8 Hz, 12H,

CH(CH3)2), 1.80 (d, 3JHH = 11.8 Hz, 1H, HtransC(Hcis)CHCHPh), 3.02-3.32 (br m, 5H,

CH(CH3)2 & HcisC(Htrans)CHCHPh), 4.24 (d, 3JHH = 12.5 Hz, 1H, CH2CHCHPh), 5.00 (m,

1H, CH2CHCHPh), 7.01-7.24 (m, 11H, ArH). 13

C NMR (75.47 MHz, CDCl3) δ 24.46 (s,

CH(CH3)2), 25.25 (s, CH(CH3)2), 28.81 (s, CH(CH3)2), 49.39 (s, CH2CHC(H)Ph), 90.81 (s,

CH2CHC(H)Ph), 108.95 (s, CH2CHC(H)Ph), 111.06 (s, NCBr), 124.60, 127.09, 127.74,

128.38, 130.81, 134.85, 137.75, 146.81 (s, ArC & ArCH), 190.39 (s, NCN). IR (Nujol) ν/cm-

1 666 (sh w), 688 (sh m), 751 (m), 823 (m), 933 (sh w), 1041 (sh w), 1057 (w), 1158 (w), 1178

(sh w), 1229 (sh w), 1269 (sh w), 1293 (m), 1351 (s), 1584 (sh w), 1622 (sh w). Anal. Calc.

for C36H43Br2ClN2Pd: C, 53.68; H, 5.38; N, 3.48. Found: C, 54.13; H, 5.49; N, 3.47 %.

[PdCl(η3-Cin)(IMesBr)] (4

IMesBr)

IMesBr (120 mg, 260 µmol) and [{Pd(µ-Cl)(η3-Cin)}2] (65 mg, 125 µmol) yielded the title

compound as yellow petaloids (124 mg, 172 µmol, 69%), dec. 199 °C. 1H NMR (300.13

MHz, C6D6) δ 2.01 (d, 3JHH = 12.1 Hz, 1H, HtransC(Hcis)CHCHPh), 2.05 (s, 6H, o- or p-CH3),

2.24 (s, 6H, o- or p-CH3), 2.30 (s, 6H, o- or p-CH3), 3.16 (d, 3JHH = 6.4 Hz, 1H,

HcisC(Htrans)CHCHPh), 4.27 (d, 3JHH = 12.6 Hz, 1H, CH2CHCHPh), 5.05 (m, 1H,

CH2CHCHPh), 6.73 (br s, 4H, m-ArH, IMesBr), 6.84-7.06 (m, 5H, ArH, Ph). 13

C NMR

(75.47 MHz, CDCl3) δ 18.32 (br s, FWHM 2.4 Hz, o- or p-CH3), 20.84 (s, FWHM 1.3 Hz, o-

or p-CH3), 47.07 (s, CH2CHC(H)Ph), 90.24 (s, CH2CHC(H)Ph), 108.82 (s, CH2CHC(H)Ph),

108.85 (s, NCBr), 126.67, 128.65, 129.34, 134.73, 136.13, 136.37, 138.02, 139.63 (s, ArC &

NCH), 188.73 (s, NCN). IR (Nujol) ν/cm-1

666 (sh m), 695 (sh m), 754 (sh w), 855 (sh w),

969 (sh w), 1033 (w), 1146 (w), 1195 (sh w), 1300 (sh m), 1311 (sh m), 1376 (sh s), 1460 (s),

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1548 (sh w), 1608 (w). Anal. Calc. for C30H31Br2ClN2Pd: C, 49.96; H, 4.33; N, 3.88. Found:

C, 49.74; H, 4.39; N, 3.75 %.

[PdCl(η3-Cin)(IMes)] (4

IMes)

IMes (150 mg, 493 µmol) and [{Pd(µ-Cl)(η3-Cin)}2] (127 mg, 245 µmol) yielded the title

compound as crystalline pale yellow shards suitable for X-ray structure determination (220

mg, 390 µmol, 80%), dec. 186 °C. 1H NMR (300.13 MHz, C6D6) δ 1.98 (d,

3JHH = 11.7 Hz,

1H, HtransC(Hcis)CHCHPh), 2.08 (s, 6H, o- or p-CH3), 2.21 (s, 6H, o- or p-CH3), 2.28 (s, 6H,

o- or p-CH3), 3.11 (d, 3JHH = 6.7 Hz, 1H, HcisC(Htrans)CHCHPh), 4.35 (d,

3JHH = 12.7 Hz, 1H,

CH2CHCHPh), 5.11 (m, 1H, CH2CHCHPh), 6.20 (s, 2H, NCH), 6.75 (br s, 4H, ArH, IMes),

6.87-7.12 (m, 5H, ArH, Ph). 13

C NMR (75.47 MHz, CDCl3) δ 18.17 (s, o- or p-CH3), 18.23

(s, o- or p-CH3), 20.72 (s, o- or p-CH3), 45.13 (s, CH2CHC(H)Ph), 90.11 (s, CH2CHC(H)Ph),

108.50 (s, CH2CHC(H)Ph), 122.48, 126.31, 127.89, 128.98, 135.49, 135.59, 136.19, 138.23,

138.51 (s, ArC & NCH), 183.96 (s, NCN). IR (Nujol) ν/cm-1

666 (sh w), 695 (w), 723 (w),

851 (w), 928 (w), 965 (w), 1032 (br w), 1233 (w), 1274 (w), 1274 (w), 1331 (w), 1377 (sh m),

1403 (w), 1463 (s), 1487 (w), 1597 (w). Anal. Calc. for C30H33ClN2Pd: C, 63.95; H, 5.90; N,

4.97. Found: C, 64.07; H, 5.90; N, 4.95 %.

S10 | P a g e

Catalyses

The Suzuki couplings and transfer hydrogenations were conducted using a J-Kem Scientific

reactor block. Extents of conversion were calculated using specific resonance integrals in 1H

NMR spectra acquired on a Bruker DPX 300, Bruker DPX 400 or a Bruker Avance III 600

instrument in CDCl3. T1 relaxation tests were carried out on the substrates and products to

ensure sufficient pulse delays were employed and hence reliable spectrum integrals.

Suzuki coupling of naphthalene-1-boronic acid with 2-bromomesitylene with 4L

A reaction vial was charged with napthalene-1-boronic acid (206 mg, 1.20 mmol), KOtBu

(112 mg, 1.00 mmol) and 4L (1 mol %) under argon. Isopropyl alcohol (4 cm

3) was added by

syringe and the mixture stirred for 10 minutes before addition of 2-bromomesitylene (150 µL,

0.98 mmol). After two hours stirring the solvent was evaporated under a flow of nitrogen and

the resultant residue analysed by 1H NMR spectroscopy (CDCl3). Percentage extent of

conversion was determined using the integrals of the aryl bromide singlet at δ 6.89 and the

coupling product singlet at δ 7.02 (Table S1). All reactions were undertaken in duplicate with

the mean conversion used in the article.

Table S1

Catalyst Iteration 1 Iteration 2 Mean*

4IPr 94.8 95.9 95.4

4IPrBr 97.1 95.8 96.5

4IMes 31.2 31.7 31.5

4IMesBr 41.1 42.3 41.7

*Rounded mean conversion is used in Table 1of article.

S11 | P a g e

Transfer hydrogenation of acetophenone in isopropyl alcohol with 1L

A reaction vial was charged with 1L (0.1 mol %) in a glove box. Acetophenone (2.00 cm

3,

2.06g, 17.1 mmol), KOtBu solution (5.00 cm

3, 7.1 x 10

-2 M in

iPrOH, 0.355 mmol, ~2 mol

%) and isopropyl alcohol (3 cm3) were added to the vial in sequence by syringe and the

solution heated at 80 °C for 42 hours. Aliquots (0.1 cm3) were taken at 18 and 42 hours and

quenched with deuterochloroform (1.5 cm3) prior to determination of extent of conversion by

1H NMR spectroscopy (CDCl3) (see Tables S2 and S3). Due to resonance overlap in the

aromatic region the 1H NMR

spectra of the quenched reaction mixture aliquots were

referenced to the isopropyl alcohol methine signal (δ 4.04).[S9]

Percentage extent of

conversion was determined using the integrals of the acetophenone methyl singlet at δ 2.64

and the 1-phenylethanol methyl doublet at δ 1.52. All reactions were undertaken in triplicate

with the mean conversion used in the article.

Table S2

Extent of Conversion (%) at 18 Hrs

Catalyst Iteration 1 Iteration 2 Iteration 3 Average Stan. Deviation

1IPr 17.4 18.1 18.2 17.9 0.4

1IPrBr 21.3 21.1 22.5 21.6 0.8

1IMes 9.9 9.3 11.6 10.3 1.2

1IMesBr 11.6 10.8 12.9 11.8 1.1

Table S3

Extent of Conversion (%) at 42 Hrs

Catalyst Iteration 1 Iteration 2 Iteration 3 Average* Stan. Deviation

1IPr 36.3 35.5 35.8 35.9 0.4

1IPrBr 36.6 38.8 37.4 37.6 1.1

1IMes 20.8 22.6 21.4 21.6 0.9

1IMesBr 28.0 30.6 30.2 29.6 1.4

*Rounded mean conversion is used in Table 1 of article.

S12 | P a g e

Single crystal X-ray diffraction structure determinations

Crystalline samples of IPrBr∙C7H8, 1IMesBr

and 1IPrBr

∙2C7H8 were mounted on MiTeGen

liquid wicks in type NVH immersion oil at 150(2) K. A summary of crystallographic data

can be found in Table S4. Data were collected using graphite monochromated MoKα X-ray

radiation ( = 0.71073 Å) on a Bruker Apex II CCD diffractometer, and were corrected for

absorption by empirical methods using SADABS.[S10]

Unit cell parameters were determined

for collection employing software defaults and optimised upon completion of the data

collection using all collected frames. Structure solution and refinement was carried out using

the SHELX suite of programs[S11]

with the interface X-Seed.[S12]

The hydrogen atoms of all

three samples were refined in calculated positions (riding model).

Variata

The lattice toluene of IPrBr∙C7H8 exhibits a small amount of “head to tail” disorder (C(28)-

C(34)). Modelling led to unsatisfactory thermal parameters (NPD atoms). While the IPrBr

molecule in this structure is well behaved, the lattice solvent exhibits several examples of

unconventional C-C bonding (range of C(29)-C(34) contacts 0.36 Å) and prolate atoms (e.g.

C(34)).

One toluene of solvation in 1IPrBr

∙2C7H8 exhibits substantial disorder (C(43)-C(49)).

Attempts to model the disorder proved unsuccessful (NPD atoms and unstable refinement).

This resulted in a number of prolate atoms (e.g. C(46)), and unusual C-C contacts (range of

C(43)-C(48) contacts = 0.62 Å, shortest contact C(45)-C(46) 1.11 Å, longest contact C(46)-

C(47) 1.73 Å). The metal complex 1IPrBr

and remaining lattice toluene are well behaved and

do not exhibit disorder.

S13 | P a g e

Table S4

IPrBr∙C7H8 1IPrBr

∙2C7H8 1IMesBr

CCDC Deposition # 831266 831265 831264

Mol. Formula C27H34Br2N2∙C7H8 C35H48Br2ClIrN2∙2C7H8 C29H34Br2ClIrN2

Mol. Weight 638.52 1066.48 798.05

Crystal System Triclinic Monoclinic Monoclinic

Space Group P-1 P21/c P21/c

a, Å 10.4613(10) 10.6872(13) 12.9409(3)

b, Å 11.4351(9) 21.9371(16) 11.8975(3)

c, Å 15.2078(11) 19.3647(14) 19.1295(5)

, deg 77.020(3) 90 90

β, deg 76.084(4) 99.668(3) 109.4460(10)

γ, deg 70.612(4) 90 90

Volume, Å3 1644.8(2) 4475.5(7) 2777.25(12)

Z 2 4 4

Description Prism Prism Prism

Colour Colourless Dark Yellow Yellow

Dc, g cm-3

1.289 1.583 1.909

F(000) 660 2136 1544

μ, mm-1

2.487 4.864 7.802

Reflections Collected 19092 33217 31562

R(int) 0.0484 0.0835 0.0458

R(sigma) 0.0816 0.1065 0.0405

Unique

Reflections

7522 10597 7468

Parameters Varied 352 506 322

R1 0.0555 0.0642 0.0237

wR2 (all data) 0.1404 0.1497 0.0494

GoF 1.018 1.105 1.043

Δρ/e Å-3

1.373/-0.589 2.544/-3.184 0.936/-0.688

S14 | P a g e

Thermal Ellipsoid Plots

Molecular structure of IPrBr (50% thermal ellipsoids, POV-RAY illustration). All

hydrogen atoms and lattice toluene omitted for clarity. Selected bond lengths (Å) and angles

(º) with the analogous values for IPr[S13]

in square parentheses: C(1)-N(1) 1.372(5) [1.364(3)],

C(1)-N(2) 1.379(5) [1.369(3)], N(1)-C(2) 1.381(5) [1.394(3)], N(2)-C(3) 1.388(5) [1.394(3)],

C(2)-C(3) 1.328(6) [1.336(3)], Br(1)-C(2) 1.862(4), Br(2)-C(3) 1.858(4), N(1)-C(1)-N(2)

101.8(3) [101.5(2)], C(1)-N(1)-C(2) 112.3(3) [113.1(2)], C(1)-N(2)-C(3) 112.0(3) [113.0(2)],

Σ N(1) angles 359.9(9) [359.9(6)], Σ N(2) angles 360.1(9) [360.0(6)], C(4)Aryl:Hetrocycle

89.7 [78.1], C(16)Aryl:Heterocycle 86.2 [65.4], %VBur 41.5 [41.0].[S14]

S15 | P a g e

Molecular structure of 1IPrBr

(50% thermal ellipsoids, POV-RAY illustration). All

hydrogen atoms and lattice solvent omitted for clarity. Selected bond lengths (Å) and angles

(º) with the analogous values for one molecule of 1IPr[S8]

in square parentheses: Ir(1)-C(1)

2.035(8) [2.054(5)], Ir(1)-Cl(1) 2.360(3) [2.340(2)], Ir(1)-C(28)C(29)centroid 2.07 [2.07], Ir(1)-

C(32)C(33)centroid 2.00 [2.01], N(1)-C(1) 1.381(10) [1.373(7)], N(2)-C(1) 1.377(11)

[1.368(6)], C(2)-C(3) 1.347(12) [1.318(8)], N(1)-C(1)-N(2) 103.5(7) [103.2(4)], C(1)-Ir(1)-

Cl(1) 87.8(3) [86.5(1)], C(1)-Ir(1)-C(32)C(33)centroid 96.5 [97.7], C(1)-Ir(1)-C(28)C(29)centroid

176.0 [175.6], C(1)-N(1)-C(2) 111.5(7) [110.8(5)], C(1)-N(2)-C(3) 110.7(7) [110.9(5)], N(1)-

C(2)-C(3) 106.8(7) [107.3(5)], N(2)-C(3)-C(2) 107.4(8) [107.8(5)], Cl(1)-Ir(1)-

C(28)C(29)centroid 88.1 [89.3], Cl(1)-Ir(1)-C(32)C(33)centroid 175.6 [175.0], IPrBr %SolidG

38.49 [38.89],[S15]

%VBur 34.1 [35.0].[S14]

S16 | P a g e

Molecular structure of 1IMesBr

(50% thermal ellipsoids, POV-RAY illustration). All

hydrogen atoms omitted for clarity. Selected bond lengths (Å) and angles (º) with the

analogous values for one molecule of 1IMes[S8]

in square parentheses: Ir(1)-C(1) 2.042(3)

[2.055(5)], Ir(1)-Cl(1) 2.3773(7) [2.353(1)], Ir(1)-C(22)C(23)centroid 2.00 [2.00], Ir(1)-

C(26)C(27)centroid 2.08 [2.07], N(1)-C(1) 1.372(3) [1.367(6)], N(2)-C(1) 1.374(3) [1.368(7)],

C(2)-C(3) 1.342(4) [1.331(8)], N(1)-C(1)-N(2) 103.6(2) [103.1(4)], C(1)-Ir(1)-Cl(1)

90.22(7) [89.8(1)], C(1)-Ir(1)-C(26)C(27)centroid 174.9 [175.3], C(1)-Ir(1)-C(22)C(23)centroid

95.6 [94.8], C(1)-N(1)-C(2) 111.2(2) [111.3(4)], C(1)-N(2)-C(3) 111.1(2) [111.5(4)], N(1)-

C(2)-C(3) 107.3(2) [107.4(4)], N(2)-C(3)-C(2) 106.8(2) [106.6(4)], Cl(1)-Ir(1)-

C(22)C(23)centroid 172.2 [172.9], Cl(1)-Ir(1)-C(26)C(27)centroid 88.3 [89.3], IMesBr %SolidG

33.33 [32.83],[S15]

%VBur 33.2 [31.9].[S14]

S17 | P a g e

Solid angle data for 1L complexes as determined by the program Solid-

G[S15]

Complex 1IPrBr

+-----------------------------------------------------------------------------+

| Program Solid-G. Ver 0.25, October 09, 2006. |

| The Molecular Structure Laboratory |

| Chemistry Department, University of Wisconsin-Madison |

|-----------------------------------------------------------------------------|

| Structure from [IrClCOD(IPrBr)].xyz on 8/13/2014 3:28:16 PM |

+-----------------------------------------------------------------------------+

COPY OF Table 7. Normalization to M-L=2.28 Angstrems

-------------------------------------------------------------------------------

Ligand | Omega(L) | G2.28(L) | Equivalent Cone Angle (ECA)

| Steradians | Percent | Degrees

-------------------------------------------------------------------------------

1 | 1.81 | 14.38 | 89.14

2 | 4.84 | 38.49 | 153.37 3 | 3.64 | 28.93 | 130.16

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,

Omega(L) - Solid Angle of the Ligand normalized to M-L=2.28 A,

G2.28(L) - The normalized percentage of the sphere shielded by the ligand,

ECA - Cone angle corresponding to the Omega(L) and not

Tolman's cone angle for the ligand. The ECA is always smaller

than Tolman's cone angle since this program does not assume

free rotation about the M-L axis.

-------------------------------------------------------------------------------

S18 | P a g e

Table 1. Complex composition, atomic coordinates and radii

-------------------------------------------------------------------------------

Atom L X Y Z Cov vdW ZER

-------------------------------------------------------------------------------

Ir1 0 -0.0000 -0.0000 0.0000 1.866 1.953 1.598

Cl1 1* 1.8436 -0.4785 -1.3931 0.750 1.900 1.600

Br1 2 -2.9209 0.0877 -5.1201 1.035 2.146 1.845

Br2 2 -2.4938 -3.4028 -4.1767 1.035 2.146 1.845

N1 2 -1.7506 0.1584 -2.4988 0.630 1.773 1.521

N2 2 -1.4368 -1.9164 -1.9612 0.630 1.773 1.521

C1 2* -1.2074 -0.6367 -1.5086 0.670 1.825 1.539

C2 2 -2.2407 -0.6022 -3.5520 0.670 1.825 1.539

C3 2 -2.0512 -1.8939 -3.2195 0.670 1.825 1.539

C4 2 -2.0273 1.5789 -2.3303 0.670 1.825 1.539

C5 2 -1.0199 2.5007 -2.6395 0.670 1.825 1.539

C6 2 -1.3220 3.8406 -2.4310 0.670 1.825 1.539

H6 2 -0.6645 4.4990 -2.6227 0.371 1.675 1.000

C7 2 -2.5482 4.2373 -1.9543 0.670 1.825 1.539

H7 2 -2.7220 5.1590 -1.8038 0.371 1.675 1.000

C8 2 -3.5239 3.3051 -1.6944 0.670 1.825 1.539

H8 2 -4.3735 3.5958 -1.3841 0.371 1.675 1.000

C9 2 -3.2938 1.9406 -1.8764 0.670 1.825 1.539

C10 2 0.2984 2.1049 -3.2671 0.670 1.825 1.539

H10 2 0.4337 1.1250 -3.1205 0.371 1.675 1.000

C11 2 1.4835 2.8481 -2.6563 0.670 1.825 1.539

H11a 2 1.4597 3.7870 -2.9362 0.371 1.675 1.000

H11b 2 2.3193 2.4373 -2.9616 0.371 1.675 1.000

H11c 2 1.4325 2.7973 -1.6790 0.371 1.675 1.000

C12 2 0.1989 2.3551 -4.7725 0.670 1.825 1.539

H12a 2 -0.5635 1.8584 -5.1365 0.371 1.675 1.000

H12b 2 1.0232 2.0542 -5.2088 0.371 1.675 1.000

H12c 2 0.0731 3.3130 -4.9368 0.371 1.675 1.000

C13 2 -4.4284 0.9681 -1.6257 0.670 1.825 1.539

H13 2 -4.0669 0.0472 -1.7717 0.371 1.675 1.000

C14 2 -4.9728 1.0183 -0.2091 0.670 1.825 1.539

H14a 2 -4.2482 0.8392 0.4259 0.371 1.675 1.000

H14b 2 -5.6737 0.3415 -0.1043 0.371 1.675 1.000

H14c 2 -5.3479 1.9067 -0.0346 0.371 1.675 1.000

C15 2 -5.5852 1.1620 -2.6082 0.670 1.825 1.539

H15a 2 -6.2343 0.4364 -2.4959 0.371 1.675 1.000

H15b 2 -5.2399 1.1524 -3.5253 0.371 1.675 1.000

H15c 2 -6.0223 2.0214 -2.4327 0.371 1.675 1.000

C16 2 -1.3247 -3.1523 -1.1888 0.670 1.825 1.539

C17 2 -2.4113 -3.4818 -0.3507 0.670 1.825 1.539

C18 2 -2.3417 -4.7214 0.2832 0.670 1.825 1.539

H18 2 -3.0452 -4.9843 0.8649 0.371 1.675 1.000

C19 2 -1.2849 -5.5692 0.0884 0.670 1.825 1.539

H19 2 -1.2691 -6.4090 0.5323 0.371 1.675 1.000

C20 2 -0.2505 -5.2220 -0.7380 0.670 1.825 1.539

H20 2 0.4673 -5.8308 -0.8669 0.371 1.675 1.000

C21 2 -0.2299 -3.9950 -1.3926 0.670 1.825 1.539

C22 2 -3.6312 -2.5872 -0.1667 0.670 1.825 1.539

H22 2 -3.3571 -1.6466 -0.3670 0.371 1.675 1.000

C23 2 -4.1453 -2.6330 1.2778 0.670 1.825 1.539

H23a 2 -4.5732 -3.4986 1.4450 0.371 1.675 1.000

H23b 2 -4.7973 -1.9144 1.4154 0.371 1.675 1.000

H23c 2 -3.3940 -2.5151 1.8959 0.371 1.675 1.000

S19 | P a g e

C24 2 -4.7468 -2.9718 -1.1415 0.670 1.825 1.539

H24a 2 -4.4163 -2.8993 -2.0612 0.371 1.675 1.000

H24b 2 -5.5093 -2.3683 -1.0199 0.371 1.675 1.000

H24c 2 -5.0291 -3.8940 -0.9676 0.371 1.675 1.000

C25 2 0.9561 -3.6628 -2.2988 0.670 1.825 1.539

H25 2 0.8620 -2.7174 -2.6108 0.371 1.675 1.000

C26 2 2.2784 -3.7959 -1.5483 0.670 1.825 1.539

H26a 2 3.0228 -3.6748 -2.1741 0.371 1.675 1.000

H26b 2 2.3350 -4.6858 -1.1416 0.371 1.675 1.000

H26c 2 2.3264 -3.1127 -0.8474 0.371 1.675 1.000

C27 2 0.9777 -4.5791 -3.5251 0.670 1.825 1.539

H27a 2 1.1613 -5.4992 -3.2422 0.371 1.675 1.000

H27b 2 1.6778 -4.2815 -4.1430 0.371 1.675 1.000

H27c 2 0.1079 -4.5432 -3.9752 0.371 1.675 1.000

C28 3* 1.3193 -0.0159 1.7549 0.670 1.825 1.539

H28 3 1.8127 -0.7247 1.3591 0.371 1.675 1.000

C29 3* 1.3586 1.2381 1.1413 0.670 1.825 1.539

H29 3 1.8828 1.3193 0.3531 0.371 1.675 1.000

C30 3 0.6415 2.4736 1.6213 0.670 1.825 1.539

H30a 3 1.0995 2.8181 2.4286 0.371 1.675 1.000

H30b 3 0.6983 3.1710 0.9211 0.371 1.675 1.000

C31 3 -0.7903 2.2291 1.9451 0.670 1.825 1.539

H31a 3 -1.2927 3.0746 1.8312 0.371 1.675 1.000

H31b 3 -0.8620 1.9621 2.8957 0.371 1.675 1.000

C32 3* -1.4369 1.1514 1.0803 0.670 1.825 1.539

H32 3 -1.8143 1.3973 0.2439 0.371 1.675 1.000

C33 3* -1.4933 -0.2376 1.4962 0.670 1.825 1.539

H33 3 -1.9497 -0.8543 0.9360 0.371 1.675 1.000

C34 3 -0.8717 -0.7568 2.7615 0.670 1.825 1.539

H34a 3 -1.4375 -0.4772 3.5242 0.371 1.675 1.000

H34b 3 -0.8829 -1.7462 2.7310 0.371 1.675 1.000

C35 3 0.5273 -0.3108 3.0262 0.670 1.825 1.539

H35a 3 0.9965 -1.0149 3.5403 0.371 1.675 1.000

H35b 3 0.5032 0.5055 3.5857 0.371 1.675 1.000

-------------------------------------------------------------------------------

Legend:

L - ligand #, atoms connected to Ir1 are marked with a *,

X,Y,Z, - Cartesian coordinates,

Cov - covalent radius,

vdW, - van der Waals radius,

ZER - Zero Energy Radius, at R(E=0)

-------------------------------------------------------------------------------

S20 | P a g e

Table 2. Ligand Composition and Coordination

-------------------------------------------------------------------------------

Ligand | H | Atoms | Formula | Ir1-L | Coordinated atoms

-------------------------------------------------------------------------------

1 | 1 | 1 | Cl1 | 2.360 | Cl1

2 | 1 | 65 | H34C27N2Br2 | 2.034 | C1

3 | 4 | 20 | H12C8 | 1.470 | C28 C29 C32 C33

-------------------------------------------------------------------------------

Legend:

Ligand - ligand number,

H - ligand hapticity,

Atoms - number of atoms in the ligand,

Ir1-L - distance between Ir1 and the geometrical center of the

shape formed by the coordinated atoms,

CA - list of atoms coordinated to Ir1.

-------------------------------------------------------------------------------

Table 3. Coordinated Atom Data

-------------------------------------------------------------------------------

Atom | Ir1 -Atom Distance | Atom Solid Angle | Atom Cone Angle

| Angstroms | Steradians | Degrees

-------------------------------------------------------------------------------

Cl1 | 2.3598 | 1.66 | 85.38

C1 | 2.0345 | 2.17 | 98.31

C28 | 2.1956 | 1.80 | 89.01

C29 | 2.1636 | 1.87 | 90.68

C32 | 2.1348 | 1.93 | 92.26

C33 | 2.1272 | 1.95 | 92.69

-------------------------------------------------------------------------------

Table 3. Calculated 6-membered Ring(s)

-------------------------------------------------------------------------------

Ring | Atoms | Centroid | ZER

-------------------------------------------------------------------------------

1 | C4 C5 C6 C7 C8 C9 | Da1 | 0.000

2 | C16 C17 C18 C19 C20 C21 | Da2 | 0.000

-------------------------------------------------------------------------------

Legend:

Ring - Ring number,

Atoms - Atoms forming the ring,

Da# - Name of the dummy atom in the center of the ring,

ZER - R(E=0), Atomic Zero Energy Radius for atom Da#.

-------------------------------------------------------------------------------

S21 | P a g e

Table 4. Calculated NEW 8-membered Ring(s)

-------------------------------------------------------------------------------

Ring | Atoms | Centroid | REMO

-------------------------------------------------------------------------------

1 | C28 C29 C30 C31 C32 C33 C34 C35 | Da3 | 0.383

-------------------------------------------------------------------------------

Legend:

Ring - Ring number,




-------------------------------------------------------------------------------

Table 5. Ligand Angle Calculations

-------------------------------------------------------------------------------

Ligand | Omega(L) | G(L) | Equivalent Cone Angle (ECA)

# | Steradians | Percent | Degrees

-------------------------------------------------------------------------------

1 | 1.66 | 13.24 | 85.34

2 | 5.19 | 41.31 | 159.99

3 | 5.69 | 45.29 | 169.19

-------------------------------------------------------------------------------

SUM(G(L)) | 12.55 | 99.84 |

G(complex) | 11.49 | 91.47 |

G(gamma) | 1.05 | 8.37 |

-------------------------------------------------------------------------------

G(Ir1 ) | 9.29 | 73.90 | Cl1 C1 C28 C29 C32 C33

-------------------------------------------------------------------------------

S(Ir1 ) | 9.20 | 73.24 | Cl1 C1 C28 C29 C32 C33

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,

Omega(L) - Solid Angle of the Ligand,

G(L) - The percentage of the sphere shielded by the ligand,


Tolman's cone angle for the ligand. The ECA is usually smaller than

Tolman's cone angle since this program does not assume


SUM(G(L)) - The sum of all individual ligand G(L) values,

G(complex) - The G value for the complex, all ligands treated as one,

G(gamma) - The percentage of the sphere shielded by more than one ligand.

G(Ir1 ) - The percentage of Ir1 's surface

shielded by the ligated atoms only,

S(Ir1 ) - The percentage of Ir1 's surface

"in contact" with the ligated atoms.

-------------------------------------------------------------------------------

S22 | P a g e

Table 6. Unfavorable Close Contacts Between Atoms

-------------------------------------------------------------------------------

Atom, Lig & Atom, Lig | Separat | SUM | Violation | Omega(O)|G(gamma)| Volume

name, # & name, # | Ang | Ang | Ang | sr | % | Ang^3

-------------------------------------------------------------------------------

Cl1 1 - H29 3 | 2.507 | 2.600 | 0.093 | 0.02 | 0.12 | 0.02

-------------------------------------------------------------------------------

Total | 0.02 | 0.12 | 0.02

-------------------------------------------------------------------------------

Legend:

Separat - Separation between the atoms in Angstroms,

SUM - the sum of the element Zero Energy radii in Angstroms,

Violation = SUM - Separation, in Angstroms,

Omega(O) - The solid angle of the overlap, steradians,

G(gamma) - The percentage of the sphere shielded by the overlap, %

Volume - Volume of the disk formed by the overlapping ZER spheres,

cubic Angstroms.

-------------------------------------------------------------------------------

Table 7. Normalization to M-L=2.28 Angstrems

-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

1 | 1.81 | 14.38 | 89.14

2 | 4.84 | 38.49 | 153.37 3 | 3.64 | 28.93 | 130.16

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,







-------------------------------------------------------------------------------

+-----------------------------------------------------------------------------+

| Output written to [IrClCOD(IPrBr)].out. |

| Computation Time: 3.63 seconds. Completed on 8/13/2014 3:28:20 PM |

+-----------------------------------------------------------------------------+

S23 | P a g e

Complex 1IPr[S8]

+-----------------------------------------------------------------------------+




|-----------------------------------------------------------------------------|

| Structure from [IrClCOD(IPr)]_SolidAngle.xyz on 8/13/2014 11:15:17 AM |

+-----------------------------------------------------------------------------+


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

1 | 1.81 | 14.38 | 89.14

2 | 4.89 | 38.89 | 154.33 3 | 3.64 | 28.94 | 130.18

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,







-------------------------------------------------------------------------------

S24 | P a g e


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

Ir1 0 -0.0000 -0.0000 -0.0000 1.866 1.953 1.598

Cl1 1* -2.1875 -0.7636 -0.3243 0.750 1.900 1.600

N1 2 0.3914 -3.0187 -0.5395 0.630 1.773 1.521

C1 2* 0.5024 -1.9640 0.3332 0.670 1.825 1.539

N2 2 0.8706 -2.5667 1.5053 0.630 1.773 1.521

C2 2 0.6983 -4.2094 0.0884 0.670 1.825 1.539

H2 2 0.7108 -5.0712 -0.3102 0.371 1.675 1.000

C3 2 0.9708 -3.9291 1.3468 0.670 1.825 1.539

H3 2 1.1954 -4.5560 2.0236 0.371 1.675 1.000

C4 2 0.0422 -2.9945 -1.9536 0.670 1.825 1.539

C5 2 -1.2187 -3.4887 -2.3433 0.670 1.825 1.539

C6 2 -1.4638 -3.5224 -3.7021 0.670 1.825 1.539

H6 2 -2.3065 -3.8385 -4.0073 0.371 1.675 1.000

C7 2 -0.5420 -3.1188 -4.6223 0.670 1.825 1.539

H7 2 -0.7541 -3.1441 -5.5484 0.371 1.675 1.000

C8 2 0.6979 -2.6731 -4.2129 0.670 1.825 1.539

H8 2 1.3400 -2.4086 -4.8631 0.371 1.675 1.000

C9 2 1.0244 -2.6078 -2.8612 0.670 1.825 1.539

C10 2 2.4245 -2.1958 -2.4322 0.670 1.825 1.539

H10 2 2.3825 -1.9535 -1.4623 0.371 1.675 1.000

C11 2 3.4068 -3.3569 -2.5737 0.670 1.825 1.539

H11a 2 3.0841 -4.1219 -2.0514 0.371 1.675 1.000

H11b 2 4.2872 -3.0830 -2.2440 0.371 1.675 1.000

H11c 2 3.4781 -3.6119 -3.5183 0.371 1.675 1.000

C12 2 2.9332 -0.9578 -3.1997 0.670 1.825 1.539

H12a 2 3.0702 -1.1906 -4.1407 0.371 1.675 1.000

H12b 2 3.7805 -0.6575 -2.8108 0.371 1.675 1.000

H12c 2 2.2701 -0.2381 -3.1331 0.371 1.675 1.000

C13 2 -2.2596 -4.0007 -1.3734 0.670 1.825 1.539

H13 2 -2.0185 -3.6815 -0.4584 0.371 1.675 1.000

C14 2 -3.6711 -3.5118 -1.6994 0.670 1.825 1.539

H14a 2 -3.6778 -2.5319 -1.7291 0.371 1.675 1.000

H14b 2 -4.2928 -3.8216 -1.0067 0.371 1.675 1.000

H14c 2 -3.9471 -3.8669 -2.5700 0.371 1.675 1.000

C15 2 -2.2654 -5.5422 -1.3623 0.670 1.825 1.539

H15a 2 -2.3952 -5.8752 -2.2773 0.371 1.675 1.000

H15b 2 -2.9961 -5.8625 -0.7918 0.371 1.675 1.000

H15c 2 -1.4107 -5.8699 -1.0141 0.371 1.675 1.000

C16 2 1.2010 -1.9082 2.7504 0.670 1.825 1.539

C17 2 0.1786 -1.4540 3.5924 0.670 1.825 1.539

C18 2 0.5693 -0.8882 4.7831 0.670 1.825 1.539

H18 2 -0.0958 -0.5489 5.3725 0.371 1.675 1.000

C19 2 1.8838 -0.7987 5.1491 0.670 1.825 1.539

H19 2 2.1130 -0.4214 5.9911 0.371 1.675 1.000

C20 2 2.8716 -1.2507 4.3130 0.670 1.825 1.539

H20 2 3.7818 -1.1738 4.5760 0.371 1.675 1.000

C21 2 2.5544 -1.8218 3.0834 0.670 1.825 1.539

C22 2 3.6773 -2.2906 2.1629 0.670 1.825 1.539

H22 2 3.2771 -2.4908 1.2679 0.371 1.675 1.000

C23 2 4.3052 -3.5824 2.6934 0.670 1.825 1.539

H23a 2 4.6816 -3.4212 3.5832 0.371 1.675 1.000

H23b 2 5.0157 -3.8732 2.0866 0.371 1.675 1.000

H23c 2 3.6178 -4.2789 2.7497 0.371 1.675 1.000

S25 | P a g e

C24 2 4.7563 -1.2243 1.9606 0.670 1.825 1.539

H24a 2 4.3429 -0.4025 1.6235 0.371 1.675 1.000

H24b 2 5.4179 -1.5468 1.3123 0.371 1.675 1.000

H24c 2 5.1985 -1.0421 2.8164 0.371 1.675 1.000

C25 2 -1.3001 -1.5773 3.2327 0.670 1.825 1.539

H25 2 -1.3698 -1.8470 2.2718 0.371 1.675 1.000

C26 2 -2.0478 -0.2592 3.4180 0.670 1.825 1.539

H26a 2 -2.0739 -0.0295 4.3685 0.371 1.675 1.000

H26b 2 -2.9628 -0.3540 3.0794 0.371 1.675 1.000

H26c 2 -1.5885 0.4499 2.9238 0.371 1.675 1.000

C27 2 -1.9545 -2.6700 4.0944 0.670 1.825 1.539

H27a 2 -1.9178 -2.4097 5.0391 0.371 1.675 1.000

H27b 2 -1.4760 -3.5160 3.9685 0.371 1.675 1.000

H27c 2 -2.8914 -2.7816 3.8240 0.371 1.675 1.000

C28 3* -0.7350 2.0188 0.3666 0.670 1.825 1.539

H28 3 -1.4803 1.5953 0.7789 0.371 1.675 1.000

C29 3* -0.5773 1.8471 -1.0026 0.670 1.825 1.539

H29 3 -1.2558 1.3729 -1.4697 0.371 1.675 1.000

C30 3 0.5959 2.3602 -1.8054 0.670 1.825 1.539

H30a 3 0.5645 1.9556 -2.7070 0.371 1.675 1.000

H30b 3 0.5047 3.3401 -1.9106 0.371 1.675 1.000

C31 3 1.9329 2.0652 -1.1908 0.670 1.825 1.539

H31a 3 2.2047 2.8344 -0.6288 0.371 1.675 1.000

H31b 3 2.6047 1.9693 -1.9143 0.371 1.675 1.000

C32 3* 1.9433 0.8008 -0.3365 0.670 1.825 1.539

H32 3 2.1414 -0.0274 -0.7548 0.371 1.675 1.000

C33 3* 1.6744 0.8050 1.0245 0.670 1.825 1.539

H33 3 1.7325 -0.0316 1.4716 0.371 1.675 1.000

C34 3 1.3012 1.9893 1.8699 0.670 1.825 1.539

H34a 3 2.0987 2.5604 1.9977 0.371 1.675 1.000

H34b 3 1.0125 1.6711 2.7608 0.371 1.675 1.000

C35 3 0.1850 2.8259 1.2560 0.670 1.825 1.539

H35a 3 -0.3463 3.2358 1.9828 0.371 1.675 1.000

H35b 3 0.5881 3.5582 0.7233 0.371 1.675 1.000

-------------------------------------------------------------------------------

Legend:






-------------------------------------------------------------------------------

S26 | P a g e


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

1 | 1 | 1 | Cl1 | 2.340 | Cl1

2 | 1 | 65 | H36C27N2 | 2.054 | C1

3 | 4 | 20 | H12C8 | 1.484 | C28 C29 C32 C33

-------------------------------------------------------------------------------

Legend:







-------------------------------------------------------------------------------


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

Cl1 | 2.3395 | 1.70 | 86.30

C1 | 2.0544 | 2.12 | 97.03

C28 | 2.1795 | 1.83 | 89.84

C29 | 2.1795 | 1.83 | 89.84

C32 | 2.1286 | 1.94 | 92.61

C33 | 2.1216 | 1.96 | 93.00

-------------------------------------------------------------------------------


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

1 | C4 C5 C6 C7 C8 C9 | Da1 | 0.000

2 | C16 C17 C18 C19 C20 C21 | Da2 | 0.000

-------------------------------------------------------------------------------

Legend:

Ring - Ring number,




-------------------------------------------------------------------------------


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

1 | C28 C29 C30 C31 C32 C33 C34 C35 | Da3 | 0.395

-------------------------------------------------------------------------------

Legend:

Ring - Ring number,




-------------------------------------------------------------------------------

S27 | P a g e


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

1 | 1.70 | 13.51 | 86.28

2 | 5.21 | 41.46 | 160.33

3 | 5.66 | 45.03 | 168.60

-------------------------------------------------------------------------------

SUM(G(L)) | 12.57 | 100.00 |

G(complex) | 11.50 | 91.49 |

G(gamma) | 1.07 | 8.52 |

-------------------------------------------------------------------------------

G(Ir1 ) | 9.21 | 73.30 | Cl1 C1 C28 C29 C32 C33

-------------------------------------------------------------------------------

S(Ir1 ) | 9.14 | 72.72 | Cl1 C1 C28 C29 C32 C33

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,














-------------------------------------------------------------------------------

S28 | P a g e


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

Cl1 1 - H29 3 | 2.597 | 2.600 | 0.003 | 0.00 | 0.03 | 0.00

C16 2 - H33 3 | 2.332 | 2.539 | 0.207 | 0.08 | 0.64 | 0.08

-------------------------------------------------------------------------------

Total | 0.08 | 0.67 | 0.08

-------------------------------------------------------------------------------

Legend:







cubic Angstroms.

-------------------------------------------------------------------------------


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

1 | 1.81 | 14.38 | 89.14

2 | 4.89 | 38.89 | 154.33

3 | 3.64 | 28.94 | 130.18

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,







-------------------------------------------------------------------------------

+-----------------------------------------------------------------------------+

| Output written to [IrClCOD(IPr)]_SolidAngle.out. |

| Computation Time: 3.88 seconds. Completed on 8/13/2014 11:15:21 AM |

+-----------------------------------------------------------------------------+

S29 | P a g e

Complex 1IMesBr

+-----------------------------------------------------------------------------+




|-----------------------------------------------------------------------------|

| Structure from [IrClCOD(IMesBr)].xyz on 8/13/2014 3:08:55 PM |

+-----------------------------------------------------------------------------+


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

1 | 1.81 | 14.37 | 89.12

2 | 4.19 | 33.33 | 141.05 3 | 3.66 | 29.13 | 130.65

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,







-------------------------------------------------------------------------------

S30 | P a g e


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

Ir1 0 -0.0000 0.0000 0.0000 1.866 1.953 1.598

Cl1 1* -0.9207 -2.0743 0.7078 0.750 1.900 1.600

Br1 2 -3.9087 -0.8315 -4.3380 1.035 2.146 1.845

Br2 2 -0.5553 -0.9923 -5.8808 1.035 2.146 1.845

N1 2 -2.0654 -0.4233 -2.1941 0.630 1.773 1.521

N2 2 -0.1024 -0.4761 -3.0884 0.630 1.773 1.521

C1 2* -0.7346 -0.3065 -1.8804 0.670 1.825 1.539

C2 2 -2.2422 -0.6652 -3.5480 0.670 1.825 1.539

C3 2 -1.0231 -0.7102 -4.1080 0.670 1.825 1.539

C4 2 -3.1910 -0.3758 -1.2881 0.670 1.825 1.539

C5 2 -3.6605 0.8663 -0.8522 0.670 1.825 1.539

C6 2 -4.8290 0.8798 -0.0918 0.670 1.825 1.539

H6 2 -5.1538 1.7080 0.2415 0.371 1.675 1.000

C7 2 -5.5269 -0.2769 0.1901 0.670 1.825 1.539

C8 2 -5.0213 -1.4898 -0.2464 0.670 1.825 1.539

H8 2 -5.4847 -2.2892 -0.0255 0.371 1.675 1.000

C9 2 -3.8560 -1.5713 -0.9978 0.670 1.825 1.539

C10 2 -2.9847 2.1590 -1.2011 0.670 1.825 1.539

H10a 2 -3.6498 2.8783 -1.2288 0.371 1.675 1.000

H10b 2 -2.5556 2.0770 -2.0784 0.371 1.675 1.000

H10c 2 -2.3071 2.3666 -0.5242 0.371 1.675 1.000

C11 2 -6.8287 -0.2278 0.9534 0.670 1.825 1.539

H11a 2 -7.0035 0.6922 1.2423 0.371 1.675 1.000

H11b 2 -6.7692 -0.8110 1.7386 0.371 1.675 1.000

H11c 2 -7.5584 -0.5326 0.3746 0.371 1.675 1.000

C12 2 -3.3622 -2.9166 -1.4778 0.670 1.825 1.539

H12a 2 -3.5122 -3.5878 -0.7797 0.371 1.675 1.000

H12b 2 -2.4042 -2.8609 -1.6770 0.371 1.675 1.000

H12c 2 -3.8498 -3.1735 -2.2881 0.371 1.675 1.000

C13 2 1.3283 -0.5141 -3.3052 0.670 1.825 1.539

C14 2 2.0235 -1.6435 -2.8722 0.670 1.825 1.539

C15 2 3.4094 -1.6395 -3.0097 0.670 1.825 1.539

H15 2 3.9068 -2.3858 -2.6964 0.371 1.675 1.000

C16 2 4.0861 -0.5720 -3.5936 0.670 1.825 1.539

C17 2 3.3426 0.5056 -4.0607 0.670 1.825 1.539

H17 2 3.7939 1.2262 -4.4845 0.371 1.675 1.000

C18 2 1.9580 0.5631 -3.9277 0.670 1.825 1.539

C19 2 1.3049 -2.8283 -2.2842 0.670 1.825 1.539

H19a 2 1.9523 -3.5358 -2.0824 0.371 1.675 1.000

H19b 2 0.6455 -3.1627 -2.9275 0.371 1.675 1.000

H19c 2 0.8491 -2.5578 -1.4600 0.371 1.675 1.000

C20 2 5.5840 -0.5919 -3.7255 0.670 1.825 1.539

H20a 2 5.9882 -0.7124 -2.8409 0.371 1.675 1.000

H20b 2 5.8893 0.2556 -4.1114 0.371 1.675 1.000

H20c 2 5.8507 -1.3319 -4.3100 0.371 1.675 1.000

C21 2 1.2057 1.7650 -4.4263 0.670 1.825 1.539

H21a 2 1.8021 2.5426 -4.4362 0.371 1.675 1.000

H21b 2 0.4458 1.9436 -3.8340 0.371 1.675 1.000

H21c 2 0.8789 1.5924 -5.3340 0.371 1.675 1.000

C22 3* 1.5539 1.2858 -0.6240 0.670 1.825 1.539

H22 3 1.5209 0.8449 -1.4648 0.371 1.675 1.000

C23 3* 0.4394 2.0719 -0.2765 0.670 1.825 1.539

H23 3 -0.2998 2.0977 -0.8727 0.371 1.675 1.000

S31 | P a g e

C24 3 0.3619 2.8857 1.0142 0.670 1.825 1.539

H24a 3 1.2775 3.1268 1.3033 0.371 1.675 1.000

H24b 3 -0.1340 3.7249 0.8415 0.371 1.675 1.000

C25 3 -0.3325 2.1117 2.1342 0.670 1.825 1.539

H25a 3 -0.0348 2.4697 3.0079 0.371 1.675 1.000

H25b 3 -1.3102 2.2516 2.0664 0.371 1.675 1.000

C26 3* -0.0415 0.6338 2.0823 0.670 1.825 1.539

H26 3 -0.7743 0.0448 2.2184 0.371 1.675 1.000

C27 3* 1.1930 0.0572 1.8550 0.670 1.825 1.539

H27 3 1.2267 -0.8911 1.8095 0.371 1.675 1.000

C28 3 2.4922 0.8015 1.6726 0.670 1.825 1.539

H28a 3 3.2285 0.2704 2.0674 0.371 1.675 1.000

H28b 3 2.4441 1.6623 2.1592 0.371 1.675 1.000

C29 3 2.8025 1.0727 0.2104 0.670 1.825 1.539

H29a 3 3.3755 1.8775 0.1457 0.371 1.675 1.000

H29b 3 3.3114 0.3081 -0.1591 0.371 1.675 1.000

-------------------------------------------------------------------------------

Legend:






-------------------------------------------------------------------------------


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

1 | 1 | 1 | Cl1 | 2.377 | Cl1

2 | 1 | 47 | H22C21N2Br2 | 2.042 | C1

3 | 4 | 20 | H12C8 | 1.490 | C22 C23 C26 C27

-------------------------------------------------------------------------------

Legend:







-------------------------------------------------------------------------------

S32 | P a g e


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

Cl1 | 2.3773 | 1.64 | 84.60

C1 | 2.0419 | 2.15 | 97.82

C22 | 2.1112 | 1.98 | 93.60

C23 | 2.1360 | 1.93 | 92.20

C26 | 2.1770 | 1.84 | 89.97

C27 | 2.2063 | 1.78 | 88.46

-------------------------------------------------------------------------------


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

1 | C4 C5 C6 C7 C8 C9 | Da1 | 0.000

2 | C13 C14 C15 C16 C17 C18 | Da2 | 0.000

-------------------------------------------------------------------------------

Legend:

Ring - Ring number,




-------------------------------------------------------------------------------


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

1 | C22 C23 C24 C25 C26 C27 C28 C29 | Da3 | 0.419

-------------------------------------------------------------------------------

Legend:

Ring - Ring number,




-------------------------------------------------------------------------------

S33 | P a g e


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

1 | 1.64 | 13.03 | 84.64

2 | 4.53 | 36.05 | 147.59

3 | 5.66 | 45.06 | 168.67

-------------------------------------------------------------------------------

SUM(G(L)) | 11.83 | 94.14 |

G(complex) | 11.15 | 88.74 |

G(gamma) | 0.68 | 5.40 |

-------------------------------------------------------------------------------

G(Ir1 ) | 9.20 | 73.19 | Cl1 C1 C22 C23 C26 C27

-------------------------------------------------------------------------------

S(Ir1 ) | 9.10 | 72.38 | Cl1 C1 C22 C23 C26 C27

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,














-------------------------------------------------------------------------------


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

C13 2 - H22 3 | 2.296 | 2.539 | 0.243 | 0.10 | 0.76 | 0.11

C18 2 - H22 3 | 2.517 | 2.539 | 0.022 | 0.19 | 1.53 | 0.00

-------------------------------------------------------------------------------

Total | 0.29 | 2.29 | 0.11

-------------------------------------------------------------------------------

Legend:







cubic Angstroms.

-------------------------------------------------------------------------------

S34 | P a g e


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

1 | 1.81 | 14.37 | 89.12

2 | 4.19 | 33.33 | 141.05

3 | 3.66 | 29.13 | 130.65

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,







-------------------------------------------------------------------------------

+-----------------------------------------------------------------------------+

| Output written to [IrClCOD(IMesBr)].out. |

| Computation Time: 3.28 seconds. Completed on 8/13/2014 3:08:59 PM |

+-----------------------------------------------------------------------------+

S35 | P a g e

Complex 1IMes[S8]

+-----------------------------------------------------------------------------+




|-----------------------------------------------------------------------------|

| Structure from [IrClCOD(IMes)]_SolidAngle.xyz on 8/13/2014 12:44:44 PM |

+-----------------------------------------------------------------------------+


-------------------------------------------------------------------------------



-------------------------------------------------------------------------------

1 | 1.80 | 14.36 | 89.06

2 | 4.13 | 32.83 | 139.83

3 | 3.64 | 28.94 | 130.17

-------------------------------------------------------------------------------

Legend:

Ligand - Ligand #,







-------------------------------------------------------------------------------

S36 | P a g e


-------------------------------------------------------------------------------


-------------------------------------------------------------------------------

Ir1 0 0.0000 -0.0000 0.0000 1.866 1.953 1.598

Cl1 1* 0.0743 1.5990 1.7243 0.750 1.900 1.600

N1 2 -0.7452 2.4573 -1.7031 0.630 1.773 1.521

C1 2* 0.1816 1.5018 -1.3906 0.670 1.825 1.539

N2 2 1.2552 1.8447 -2.1661 0.630 1.773 1.521

C2 2 -0.2609 3.3347 -2.6586 0.670 1.825 1.539

H2 2 -0.7307 4.0654 -3.0393 0.371 1.675 1.000

C3 2 0.9854 2.9657 -2.9441 0.670 1.825 1.539

H3 2 1.5753 3.3853 -3.5588 0.371 1.675 1.000

C4 2 -2.0398 2.6570 -1.0871 0.670 1.825 1.539

C5 2 -2.1611 3.6699 -0.1535 0.670 1.825 1.539

C6 2 -3.4180 3.8725 0.4059 0.670 1.825 1.539

H6 2 -3.5182 4.5453 1.0682 0.371 1.675 1.000

C7 2 -4.5292 3.1369 0.0433 0.670 1.825 1.539

C8 2 -4.3669 2.1722 -0.9405 0.670 1.825 1.539

H8 2 -5.1228 1.6682 -1.2183 0.371 1.675 1.000

C9 2 -3.1299 1.9214 -1.5347 0.670 1.825 1.539

C10 2 -3.0354 0.9085 -2.6470 0.670 1.825 1.539

H10a 2 -2.3331 1.1762 -3.2746 0.371 1.675 1.000

H10b 2 -3.8939 0.8603 -3.1177 0.371 1.675 1.000

H10c 2 -2.8192 0.0306 -2.2702 0.371 1.675 1.000

C11 2 -5.8825 3.3901 0.6644 0.670 1.825 1.539

H11a 2 -5.7649 3.7471 1.5697 0.371 1.675 1.000

H11b 2 -6.3830 2.5485 0.7094 0.371 1.675 1.000

H11c 2 -6.3779 4.0365 0.1191 0.371 1.675 1.000

C12 2 -1.0110 4.5598 0.2130 0.670 1.825 1.539

H12a 2 -1.2475 5.0880 1.0026 0.371 1.675 1.000

H12b 2 -0.8117 5.1603 -0.5354 0.371 1.675 1.000

H12c 2 -0.2253 4.0099 0.4098 0.371 1.675 1.000

C13 2 2.5399 1.1762 -2.2072 0.670 1.825 1.539

C14 2 2.8184 0.3586 -3.3029 0.670 1.825 1.539

C15 2 4.0456 -0.2805 -3.3248 0.670 1.825 1.539

H15 2 4.2512 -0.8569 -4.0501 0.371 1.675 1.000

C16 2 4.9845 -0.1020 -2.3178 0.670 1.825 1.539

C17 2 4.6777 0.7542 -1.2684 0.670 1.825 1.539

H17 2 5.3202 0.8868 -0.5817 0.371 1.675 1.000

C18 2 3.4624 1.4174 -1.1874 0.670 1.825 1.539

C19 2 3.1883 2.3772 -0.0673 0.670 1.825 1.539

H19a 2 3.9228 2.3410 0.5821 0.371 1.675 1.000

H19b 2 2.3495 2.1312 0.3751 0.371 1.675 1.000

H19c 2 3.1152 3.2864 -0.4261 0.371 1.675 1.000

C20 2 6.3168 -0.7966 -2.3474 0.670 1.825 1.539

H20a 2 6.1866 -1.7444 -2.5596 0.371 1.675 1.000

H20b 2 6.7479 -0.7146 -1.4716 0.371 1.675 1.000

H20c 2 6.8846 -0.3842 -3.0315 0.371 1.675 1.000

C21 2 1.8102 0.1512 -4.4011 0.670 1.825 1.539

H21a 2 2.1600 -0.4999 -5.0454 0.371 1.675 1.000

H21b 2 1.6397 1.0026 -4.8551 0.371 1.675 1.000

H21c 2 0.9737 -0.1888 -4.0179 0.371 1.675 1.000

C22 3* -0.5878 -1.4791 -1.4138 0.670 1.825 1.539

H22 3 -0.9914 -0.7676 -1.8986 0.371 1.675 1.000

C23 3* 0.8138 -1.4791 -1.2620 0.670 1.825 1.539

H23 3 1.2985 -0.7797 -1.6813 0.371 1.675 1.000

S37 | P a g e

C24 3 1.5987 -

supporting information - royal society of chemistryair stable nhcs: a study of stereoelectronics and...

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