General Data. All manipulations were carried out under a nitrogen atmosphere using standard Schlenk techniques, unless otherwise stated. Solvents were distilled under nitrogen from sodium benzophenone (hexane, diethyl ether, THF, or calcium hydride (dichloromethane) and methanol was distilled over Mg/I 2 . The starting materials 1,2-(PPh 2 ) 2 -1,2-C 2 B 10 H 10 , 1 [Cp*MCl 2 ] 2 2 (M = Ir, Rh) were synthesized according to the literature. D 2 gas was produced from the reaction of CD 3 OD and

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... AlD 4 at -78 o C. Other chemical reagents were obtained from commercial sources and used without further purification. 1 H NMR (400 MHz) and 31 P NMR (162 MHz) spectra were obtained on a VAVCE DMX-400 spectrometer. 11 B NMR (160 MHz) was obtained on a Bruker DMX-500 spectrometer. Elemental analysis was performed on an Elementar vario EL III analyzer. IR (KBr) spectra were recorded on the Nicolet FT-IR spectrophotometer. Synthesis of 1a. [Cp*IrCl 2 ] 2 (197 mg, 0.25 mmol) was added to a solution of 1,2-(PPh 2 ) 2 -1,2-C 2 B 10 H 10 (256.3 mg, 0.5 mmol) in THF and CH 3 OH (5 mL/10 mL) at 0 o C. Maintain this temperature for 0.5 h, NaHCO 3 (43.0 mg, 0.5 mmol) was then added to the solution and the mixture was stirred for 24 h at room temperature. After removal of the solvent under vacuum, 1a was isolated by column chromatography on silica gel with elution CH 2 Cl 2 /CH 3 OH (15:1). Yield: 76% (328.3 mg). Fine yellow crystals of 1a were obtained through recrystallization from CH 2 Cl 2 -hexane at -18 o C. 1 H NMR (400 MHz, CDCl 3 , 25 o C): δ = 1.84 (d, 15H, Cp*, 4 J(P,H ) = 4.2 Hz), 7.41-7.91 ppm (m, 20H, phenyl); 11 B NMR (160 MHz, CDCl 3 , 25 o C): δ = -6.8 CDCl 3 , H 3 PO 4 , 25 o C): δ = 75.98 ppm (s, PPh 2 ); IR (KBr, disk): υ = 2567, 2535 (B-H), 1381 cm -1 (C-H); elemental analysis calcd (%) for C 36 H 45 B 9 ClP 2 Ir: C 50.01, H 5.25; found: C 50.09, H 5.29. Synthesis of 1b. A procedure analogous to the preparation of 1a was used, [Cp*RhCl 2 ] 2 (154.5 mg, Electronic Supplementary Material (ESI) for Chemical Communications This journal is