Computational Methods

All calculations were performed using the Gaussian 03 program suite. Where possible, atomic coordinates for geometry optimizations originated from X-ray diffraction data. Cyclohexyl, phenyl, and tert-butyl groups were replaced with methyl groups, and counterions were omitted. DFT calculations were carried out using the three hybrid functionals of Becke33 in conjunction with the correlation functional of Lee, Yang, and Parr (B3LYP).34,35 The 6-31G(p,d) basis set was applied to all non-metal atoms,36 and the Stuttgart effective core potential and associated basis set was used for Ir and Au.37 All calculations were spin-restricted on gas-phase molecules, with no imposed symmetry. Time-dependent calculations were initiated from the

optimized geometry using the B3LYP exchange and correlation functionals. Molecular orbitals were imaged in the program GaussView 3.0 with an isodensity of 0.04 applied.

2.5.6 Preparation of [RhIAuI(dcpm)2(CO)Cl](PF6) [1-(PF6)]

A solution of [RhI(COD)Cl]2 (186 mg, 0.377 mmol, 1.00 eq) in 10 mL of CH2Cl2 was

prepared in the glovebox and contained in a 100-mL Schlenk flask. A solution of dcpm (616 mg, 1.51 mmol, 4.00 eq) in 10 mL of CH2Cl2 was added dropwise to afford a bright orange

solution. The solution was bubbled with CO gas for 10 min (oil bubbler pressure) with no noticeable color change. At this time, AuI(tht)Cl (242 mg, 0.754 mmol, 2.00 eq) dissolved in 10 mL of CH2Cl2 was added, resulting in a lighter yellow-orange solution. The solution was stirred

at room temperature for 30 min and then filtered through a plug of glass wool in open air. A solution of NH4PF6 (307 mg, 1.89 mmol, 5.00 eq) in 20 mL of MeOH was added with stirring.

The resulting solution was concentrated by rotary evaporation to < 10 mL, resulting in the formation of a yellow-orange solid which was collected by filtration, washed with 10 mL of MeOH and dried in vacuo. Yield: 831 mg (83.1%). 1H NMR (500 MHz, CD2Cl2) δ/ppm:

2.53–2.64 (m, 2H), 2.45–2.53 (br, m, 4H), 2.21–2.30 (m, 4H), 2.14–2.20 (br, d, 2H), 1.13–2.12

(br, m, 80H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 52.9 (m, 2P), 34.8

(dm, 1JRh–P = 114 Hz, 2P), −144.1 (sept., 1JF–P = 711 Hz, 1P). UV-vis (CH2Cl2): λ/nm

(ε/(M−1 cm−1)) 263 (9700), 291 (sh) (5100), 418 (14000). IR (solid): ͠νC≡O _{= 1953 cm}−1. Anal.

Calcd. for C51H92AuClF6RhOP5: C, 46.21; H, 7.00. Found: C, 46.28; H, 6.83.

2.5.7 Preparation of [RhIAuI(dcpm)2(CO)Br](PF6) [2-(PF6)]

[RhI(COD)Br]2 (212 mg ,0.365 mmol, 1.00 eq) was dissolved in 10 mL of CH2Cl2. With

stirring, dcpm (596 mg, 1.46 mmol, 4.00 eq) in 10 mL of CH2Cl2 was added dropwise to give a

bright orange solution. CO was bubbled through the solution for 15 min with no color change. Addition of AuI(tht)Br (266 mg 0.730 mmol, 2.00 eq) dissolved in 10 mL CH2Cl2 effected a

color change to yellow. The solution was stirred under a CO atmosphere for 60 min and

afterwards filtered through a plug of glass wool. A solution of NH4PF6

(300 mg, 1.82 mmol, 5.00 eq) in 20 mL of MeOH was added, stirred for 5 min and concentrated to < 10 mL by rotary evaporation. A light orange solid was collected by filtration, washed with MeOH and dried in vacuo. Yield: 832 mg (83.2%). 1H NMR (500 MHz, CD2Cl2) δ/ppm:

2.55–2.73 (m, 6H), 2.12–2.36 (m, 6H), 1.10–2.12 (m, 80H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 52.5 (m, 2P), 33.7 (dm, 1JRh–P = 113 Hz, 2P), −144.1 (sept., 1JF–P = 711 Hz, 1P). UV-vis

(CH2Cl2): λ/nm (ε/(M−1 cm−1)) 263 (9300), 305 (6000), 423 (14000). IR (solid): ͠νC≡O _{= 1955}

cm−1. Anal. Calcd. for C51H92AuBrF6RhOP5: C, 44.71; H, 6.77; Found: C, 44.56; H, 6.65.

2.5.8 Preparation of [RhIAuI(dppm)2(CO)Cl](PF6) [3-(PF6)]

In a Schlenk flask equipped with a stir bar, [RhI_(COD)Cl]

2

(186 mg, 0.377 mmol, 1.00 eq) was dissolved in 10 mL of CH2Cl2 with stirring giving a dark

yellow solution. A sample of dppm (580 mg, 1.51 mmol, 4.00 eq) was dissolved in 10 mL of CH2Cl2 and added dropwise, causing a color change to orange. After stirring the solution at RT

for 10 min, CO was bubbled through it for 15 min. AuI(tht)Cl (242 mg, 0.754 mmol, 2.00 eq) dissolved in 10 mL CH2Cl2 was added and the solution stirred for 30 min. Addition of NH4PF6

(308 mg, 1.89 mmol, 5.00 eq) that was dissolved in 20 mL of MeOH gave an orange solution. Upon concentrating the solution to < 10 mL by rotary evaporation, an orange solid precipitated. The solid was collected by filtration, washed with methanol and dried in vacuo. Yield: 779 mg (80.9%). 1H NMR (500 MHz, CD3CN) δ/ppm: 7.89–7.91 (m, 4H), 7.79–7.86 (m, 4H), 7.64–7.71

(m, 4H), 7.39–7.60 (m, 22H), 7.21–7.27 (m, 2H), 7.05–7.12 (m, 4H), 4.15–4.30 (m, 4H).

31_P{1_{H} NMR (121.5 MHz, CD}

3CN) δ/ppm: 36.9 (m, 2P), 28.3 (dm, 1JRh–P = 120 Hz, 2P),

−143.4 (sept., 1JF–P = 706 Hz, 1P). UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 424 (15000). IR

(solid): ͠νC≡O = 1966 cm−1. Anal. Calcd. for C51H44AuClF6RhOP5: C, 47.96; H, 3.47; Found:

C, 47.58; H, 3.45.

2.5.9 Preparation of [RhIAuI(dppm)2(CO)Br](CF3SO3) [4-(OTf)]

In a Schlenk flask equipped with a stir bar, [RhI(COD)Br]2

(146 mg, 0.250 mmol, 1.00 eq) was dissolved in 6 mL of CH2Cl2 with stirring to afford a dark

yellow solution. To this solution was added dppm (384 mg, 1 mmol, 4.00 eq) dissolved in 5 mL of CH2Cl2, resulting in a color change to orange. After stirring the solution at RT for 10 min, CO

was bubbled through it for 15 min. AuI(tht)Br (183 mg, 0.500 mmol, 2.00 eq) dissolved in 5 mL

CH2Cl2 was added and the solution stirred for 30 min. Addition of NaOTf

(430 mg, 2.50 mmol, 10.0 eq) that was dissolved in 10 mL MeOH produced an orange solution. Concentrating the solution to < 10 mL by rotary evaporation caused an orange solid to

precipitate. The solid was collected by filtration, washed with methanol and dried in vacuo. Yield: 490 mg (73.9%). 1H NMR (500 MHz, CD2Cl2) δ/ppm: 7.80–7.91 (m, 4H), 7.65–7.75

(m, 4H), 7.36–7.63 (m, 22H), 7.25–7.34 (m, 4H), 7.18–7.24 (m, 2H), 7.00–7.07 (m, 4H), 4.35–4.48 (m, 2H), 4.02–4.12 (m, 2H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 32.4

(m, 2P), 24.2 (dm, 1JRh–P = 119 Hz, 2P). UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 430 (12000). IR

(solid): ͠νC≡O = 1966 cm−1. Anal. Calcd. for C52H44AuBrF3RhO4P4S: C, 47.11; H, 3.35; Found:

C, 46.86; H, 3.29.

2.5.10 Preparation of [IrIAuI(dcpm)2(CO)Cl](PF6) (5)

To a solution of [IrI(dcpm)2(CO)]Cl (1.00 g, 0.932 mmol, 1.00 eq) in 6 mL of CH2Cl2

was added a solution of AuI(tht)Cl (299 mg, 0.932 mmol, 1.00 eq) in 8 mL of CH2Cl2. The

orange solution was stirred at room temperature for 1 h, at which time a solution of NH4PF6

(228 mg, 1.40 mmol, 1.50 eq) in 15 mL of methanol was added. The solution was concentrated to < 10 mL via rotary evaporation, during which time an orange solid precipitated. The solid was collected by filtration, washed with 5 mL of methanol and dried in vacuo. Yield: 1.04 g (78.8%).

1_{H NMR (500 MHz, CD}

2Cl2) δ/ppm: 2.50–2.69 (br, m, 6H), 2.33 (br, d, 2H), 2.17–2.29

(br, m, 4H), 1.14–2.09 (br, m, 80H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 51.0 (m, 2P),

25.3 (m, 2P), −144.1 (sept., 1JF–P = 711 Hz, 1P). UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 300 (sh)

(4300), 316 (5700), 355 (2500), 431 (17000), 517 (300). IR (solid): ͠νC≡O = 1944 cm−1. Anal.

Calcd. for C51H92AuClF6IrOP5: C, 43.30; H, 6.55. Found: C, 43.37; H, 6.51.

2.5.11 Preparation of [IrIAuI(dcpm)2(CO)Br](PF6) (6)

A solution of AuI(tht)Br (327 mg, 0.895 mmol, 1.00 eq) in 8 mL of CH2Cl2 was added to

a solution of [IrI(dcpm)2(CO)]Br (1.00 g, 0.895 mmol, 1.00 eq) in 6 mL of CH2Cl2. The resulting

dark orange solution was stirred for 90 min at room temperature and then filtered through a plug of glass wool. A solution of NH4PF6 (220 mg, 1.35 mmol, 1.51 eq) in 15 mL of methanol was

added, and the resulting bright orange solution was stirred for 1 h. After concentrating to < 10 mL by rotary evaporation, an orange solid formed, which was collected by filtration, washed with 10 mL of methanol and dried in vacuo. Yield: 1.14 g (87.0%). 1H NMR (500 MHz, CD2Cl2) δ/ppm: 2.50–2.82 (br, m, 6H), 2.15–2.40 (br, m, 6H), 1.00–2.10 (br, m, 80H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 50.4 (m, 2P), 23.2 (m, 2P), −144.2 (sept., 1JF–P = 711 Hz, 1P).

UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 307 (sh) (5800), 319 (6400), 360 (2600), 437 (18000),

526 (320). IR (solid): ͠νC≡O = 1945 cm−1. Anal. Calcd. for C51H92AuBrF6IrOP5: C, 41.98; H, 6.35.

Found: C, 41.90; H, 6.36.

2.5.12 Preparation of [IrIAuI(dppm)2(CNtBu)2](PF6)2 (7)

To a solution of [Ir(COD)Cl]2 (149 mg, 0.222 mmol, 1.00 eq) in 5 mL of CH2Cl2 was

added a solution of dppm (341 mg, 0.887 mmol, 4.00 eq) in 2 mL of CH2Cl2, giving a yellow

solution. A solution of CNt_{Bu (73.7 mg, 0.887 mmol, 4.00 eq) was added immediately, initially} causing a change to a lighter yellow color, which darkened to yellow-orange as the solution was stirred for 20 min. At this time, a solution of Au(tht)Cl (142 mg, 0.443 mmol, 2.00 eq) in 2 mL of CH2Cl2 was added, giving a deep red solution which was stirred for 45 min. Addition of a

solution of NH4PF6 (180 mg, 1.10 mmol, 4.95 eq) in 20 mL of MeOH prompted an instantaneous

color change to dark green. The solution was concentrated to 5 mL, and the resulting green solid was filtered and washed with 5 mL of methanol. The crude solid was dissolved in 2 mL of CH2Cl2 and recrystallized by layering with 1 mL of methanol followed by 17 mL of diethyl

ether. After several hours, green microcrystals formed, which were separated from the

supernatant by decantation and dried in vacuo. Yield: 382 mg (53.4%). 1H NMR

(500 MHz, CD2Cl2) δ/ppm: 7.84–7.90 (m, 8H), 7.68–7.74 (m, 8H), 7.52–7.63 (m, 12H),

7.44–7.50 (m, 4H), 7.38–7.43 (m, 8H), 4.10 (br, pseudoquintet, 4H), 0.63 (s, 18H). 31P{1H}

NMR (202.5 MHz, CD2Cl2) δ/ppm: 30.0 (m, 2P), 10.4 (m, 2P), −143.9

(sept., 1JF–P = 712 Hz, 2P). UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 345 (11000), 402 (4400), 490

(26000), 606 (520). IR (solid): ͠νC≡N = 2138 cm−1. Anal. Calcd. for C60H62AuF12IrN2P6: C, 44.65;

H, 3.87; N, 1.74. Found: C, 44.39; H, 3.82; N, 1.59.

2.5.13 Preparation of [RhIIAuII(dcpm)2(CO)Cl3](PF6) [8-(PF6)]

A sample of 1-(PF6) (100 mg, 0.0750 mmol, 1.00 eq) was dissolved in 10 mL of CH2Cl2

and frozen in the coldwell of the glovebox. Upon thawing a cold solution of PhICl2

(22.0 mg 0.0800 mmol, 1.05 eq), dissolved in 10 mL of CH2Cl2, was added dropwise, giving a

dark red solution that was stirred at RT for 30 min. Addition of 18 mL of pentane afforded a red solid which was isolated by decantation and washed with 10 mL of pentane twice. Yield: 102 mg (96.9%). 1H NMR (500 MHz, CD2Cl2) δ/ppm: 3.40–3.55 (m, 2H), 3.19–3.32 (m, 2H), 2.83–3.02

(m, 4H), 2.68–2.80 (m, 2H), 2.49–2.63 (m, 4H), 1.20–2.40 (m, 78H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 37.8 (t, 2P), 20.2 (dt, 1JRh–P = 74 Hz, 2P), −144.1

(sept., 1JF–P = 711 Hz, 1P). UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 306 (26000), 372 (20000), 450

(6200). IR (solid): ͠νC≡O _{= 2030 cm}−1. Anal. Calcd. for C51H92AuCl3F6RhOP5: C, 43.87; H, 6.64;

Found: C, 44.51; H, 6.60.

2.5.14 Preparation of [RhIIAuII(dcpm)2(CO)Br3](PF6) [9-(PF6)]

In 4 mL of CH3CN 2-(PF6) (100 mg, 0.073 mmol, 1.00 eq) was dissolved. Br2

(12.2 mg, 0.0763 mmol, 1.05 eq) that was dissolved in 157 µL of CH3CN was added and the

solution stirred at RT for 15 min during which time a solid started to precipitate. The solution was concentrated at the rotary evaporator and the resulting dark solid dried in vacuo. The solid was redissolved in 2 mL of CH2Cl2 and precipitated with Et2O. The solvent was removed via

pipet and the red solid dried in vacuo. Yield: 103 mg (92.2%). 1H NMR (500 MHz, CD2Cl2) δ/ppm: 3.65–3.76 (m, 2H), 3.41–3.54 (m, 2H), 3.13–3.27 (m, 2H), 2.87–3.00 (m, 2H), 2.70–2.87

(m, 2H), 2.52–2.71 (m, 4H), 2.37 (br, d, 2H), 2.28 (br, d, 2H), 1.20–2.17 (m, 74H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 32.8 (t, 2P), 14.3 (dt, 1JRh–P = 74 Hz, 2P), −144.1 (sept., 1JF–P

= 711 Hz, 1P). UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 335 (26000), 426 (13000). IR (solid): ͠νC≡O = 2028 cm−1. Anal. Calcd. for C51H92AuBr3F6RhOP5: C, 40.04; H, 6.06; Found: C, 40.17;

H, 6.06.

2.5.15 Preparation of [RhIIAuII(dppm)2(CO)Cl3](PF6) [10-(PF6)]

PhICl2 (11.3 mg, 0.0411 mmol, 1.05 eq) was dissolved in 1 mL of CH2Cl2 and frozen in

the coldwell of the glovebox. 3-(PF6) (50.0 mg, 0.0392 mmol, 1.00 eq) was dissolved in 5 mL of

CH2Cl2 and likewise frozen. Upon thawing the solution of PhICl2 was added dropwise, effecting

a color change from yellow to deep red. The resulting solution was frozen in the coldwell again to avoid decomposition of the product which is stable below −20 °C but decomposes rapidly at RT. The instability of the product precluded determination of the isolated yield and further characterization, though NMR indicates a clean conversion. 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 27.7 (t, 2P), 11.3 (dt, 1JRh–P = 78 Hz, 2P), −143.4 (sept., 1JF–P = 708 Hz, 1P).

2.5.16 Preparation of [RhIIAuII(dppm)2(CO)Br3](CF3SO3) [11-(OTf)]

4-(OTf) (25.0 mg, 0.0188 mmol, 1.00 eq) was dissolved in 5 mL of CH2Cl2 and cooled to

−78 °C with a dry ice/acetone bath. Br2 (3.15 mg, 0.0197 mmol, 1.05 eq) in 0.167 mL of CH2Cl2

was added to the cold solution of 4 resulting in an immediate color change to dark red. The solution was kept in the cold to avoid decomposition of the product. Due to the thermal instability of the product it was not possible to determine the yield or perform further

characterization. 31_P{1_{H} NMR (121.5 MHz, CD}

2Cl2) δ/ppm: 20.5 (t, 2P), 3.4

(dt, 1JRh–P = 79 Hz, 2P).

2.5.17 Preparation of [IrIIAuII(dcpm)2(CO)Cl3](PF6) (12)

A solution of 5 (100 mg, 0.0707 mmol, 1.00 eq) in 1.5 mL of CH2Cl2 and a solution of

PhICl2 (23.3 mg, 0.0848 mmol, 1.20 eq) in 0.7 mL of CH2Cl2 were both chilled with liquid N2 in

the glovebox cold well. Once frozen, the two samples were removed, and upon melting the PhICl2 solution was added dropwise to the solution of 5. The color immediately faded to a lighter

orange, and the solution was stirred at room temperature for 3 h. Dropwise addition of 15 mL of pentane to the stirred solution yielded a yellow-orange solid, which was separated from the

supernatant by decantation and dried in vacuo. Yield: 104 mg (99.0%). 1H NMR

(500 MHz, CD2Cl2) δ/ppm: 3.62–3.73 (m, 2H), 3.08–3.22 (br, m, 4H), 2.81–2.90 (br, m, 2H),

2.68–2.77 (br, m, 2H), 2.54–2.64 (br, m, 2H), 2.44–2.51 (br, m, 2H), 2.08–2.32 (br, m, 6H), 1.20–2.05 (br, m, 72H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 31.6 (t, 2P), −11.0 (t, 2P),

−144.1 (sept., 1JP–F = 714 Hz, 1P). UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 266 (22000), 331

(23000), 396 (5800) 455 (sh) (1200). IR (solid): ͠νC≡O = 2009 cm−1. Anal. Calcd. for

C51H92AuCl3F6IrOP5: C, 41.23; H, 6.24. Found: C, 40.96; H, 6.15.

2.5.18 Preparation of [IrIIAuII(dcpm)2(CO)Br3](PF6) (13)

A sample of 6 (100 mg, 0.0685 mmol, 1.00 eq) was dissolved in 4 mL of acetonitrile. A solution of Br2 (11.5 mg, 0.0720 mmol, 1.05 eq) in 0.3 mL of acetonitrile was added dropwise.

The resulting suspension was stirred at room temperature for 30 min. All volatiles were removed by rotary evaporation to afford an orange solid, which was suspended in 15 mL of diethyl ether and collected by filtration. The product was washed with 10 mL of diethyl ether and dried in vacuo. Yield: 97 mg (87%). 1H NMR (500 MHz, CD2Cl2) δ/ppm: 3.84–3.94 (m, 2H), 3.35–3.49

(br, m, 4H), 2.88–2.96 (br, m, 2H), 2.73–2.81 (br, m, 2H), 2.33 (br, d, 2H) 2.24 (br, d, 2H), 2.08 (br, d, 2H), 1.21–2.05 (br, m, 76H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 25.7 (t, 2P),

−18.6 (t, 2P), −144.2 (sept., 1JF–P = 711 Hz, 1P). UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 283 (sh)

(16000), 305 (23000), 369 (15000), 416 (sh) (9400), 496 (sh) (1500). IR (solid): ͠νC≡O = 2007

cm−1. Anal. Calcd. for C51H92AuBr3F6IrOP5: C, 37.83; H, 5.73. Found: C, 37.59; H, 5.64.

2.5.19 Preparation of [IrIIAuII(dppm)2(CNtBu)2Cl2](PF6)2 (14)

A solution 7 (100 mg, 0.0620 mmol, 1.00 eq) in 1.5 mL of CH2Cl2 and a solution of

PhICl2 (18 mg, 0.065 mmol, 1.2 eq) in 1 mL of CH2Cl2 were prepared and frozen in the

glovebox cold well. After removing from the cold well and allowing the solution to melt, the PhICl2 solution was added dropwise, prompting an immediate color change from dark green to

bright yellow. The reaction solution was stirred in the dark for 1 h. The yellow solution was filtered through a plug of glass wool into 18 mL of pentane, which resulted in the formation of a pale yellow powder. The supernatant was decanted and the remaining solid was washed with pentane and dried in vacuo. Yield: 94 mg (90%). 1H NMR (500 MHz, CD2Cl2) δ/ppm: 7.61–7.70

(br, m, 16H), 7.46–7.56 (br, m, 24H), 5.24 (br, pseudoquintet, 4H), 1.01 (s, 18H). 31P{1H} NMR (121.5 MHz, CD2Cl2) δ/ppm: 7.7 (t, 2P), −17.6 (t, 2P), −143.9 (sept., 1JF–P = 711 Hz, 2P).

UV-vis (CH2Cl2): λ/nm (ε/(M−1 cm−1)) 257 (34000), 320 (33000), 388 (sh) (2600). IR (solid): ͠νC≡N = 2192 cm−1. Anal. Calcd. for C60H62AuCl2F12IrN2P6: C, 42.77; H, 3.71; N, 1.66. Found:

C, 42.43; H, 3.87; N, 1.60.

2.5.20 Preparation of [IrIIAuII(dppm)2(CNtBu)2Br2](PF6)2 (15)

A 10-mL Schlenk tube was charged with a solution of 7 (100 mg, 0.0620 mmol, 1.00 eq) in 2 mL of CH2Cl2 and chilled to −78 °C under an argon atmosphere. A solution of Br2

(10.4 mg, 0.0650 mmol, 1.05 eq) in 228 μL of CH2Cl2 was added dropwise, causing an

immediate color change to pale orange. The solution was allowed to warm to room temperature and stirred for 15 min. Addition of 17 mL of pentane afforded a yellow-orange solid, which was separated by decanting the supernatant and dried in vacuo. Yield: 106 mg (96.4%). 1H NMR (500 MHz, CD2Cl2) δ/ppm: 7.61–7.69 (br, m, 16H), 7.35–7.60 (br, m, 24H), 5.33–5.37

(br, m, 4H), 1.06 (s, 18H). 31P{1H} NMR (202.5 MHz, CD2Cl2) δ/ppm: 3.1 (t, 2P), −22.2 (t, 2P),

(38000). IR (solid): ͠νC≡N = 2189 cm−1. Anal. Calcd. for C60H62AuBr2F12IrN2P6: C, 40.62;

H, 3.52; N, 1.58. Found: C, 40.63; H, 3.62; N, 1.45.

2.5.21 Preparation of [RhIAuI(dcpm)2(CO)H](PF6) (16)

1-(PF6) (300 mg, 0.226 mmol, 1.00 eq) was dissolved in 10 mL of THF and the solution

frozen in the coldwell of the glovebox. Upon thawing a 1 M LiHBEt3 solution in THF

(0.238 mL, 0.238 mmol, 1.05 eq) was added. The solution was allowed to warm to RT and stirred for 1 h, giving a dark red solution. The solvent was removed in vacuo to afford a red- orange residue. The residue was triturated with 4 mL of Et2O to afford an orange solid, and

subsequently the Et2O was removed in vacuo. The resulting solid was taken up in 6 mL of

benzene and filtered through celite. Evaporation of the benzene yielded a red-orange solid, which was washed with 2 × 5 mL of Et2O to remove a dark red impurity. The resulting orange solid

was dried in vacuo. Yield: 250 mg (85.5%). 1H NMR (500 MHz, C6D6) δ/ppm: 2.63–2.77

(m, 4H), 2.33–2.48 (m, 4H), 1.98–2.33 (m, 20H), 1.00–1.96 (m, 64H), −4.40 (nonet, 1JRh–H = 2JP–H = 12 Hz, 3JP–H = 6 Hz, 1H). 31P{1H} NMR (C6D6) δ/ppm: 54.6 (m, 2P),

50.4 (dm, 1JRh–P = 137 Hz, 2P), −144.1 (sept., 1JP–F = 711 Hz, 1P). UV-vis (C6H6): λ/nm

(ε/(M−1 cm−1)) 359 (5000), 472 (16000). IR (solid): ͠νC≡O = 1948 cm−1. Anal. Calcd. for

C51H93AuF6RhOP5: C, 47.45; H, 7.26; Found: C, 47.49; H, 7.31.

In document Halogen-elimination photochemistry and oxygen-activation chemistry of late transition-metal complexes (Page 100-108)