The synthesis and properties of a series of rhodium-gold heterobimetallic complexes are described. Novel d8���d10 complexes [RhIAuI(dcpm)2(CO)X](PF6) (dcpm = bis(dicyclohexylphosphino)methane, X = Cl, Br) are oxidized by halogen to afford thermally stable d7�d9 metal-metal bonded RhIIAuII complexes. The presence of a formal metal-metal bond is confirmed by X-ray crystallography. The optical properties of the oxidized complexes are dominated in the UV-vis region by metal-metal s?s* transitions with admixed LMCT character, and irradiation of the complexes in the presence of a suitable halogen trap leads to clean two-electron photochemical reduction. Treatment of the RhIAuI chloride complex with lithium triethylborohydride affords the corresponding hydride-bound complex. The reactions of this species with acid halide and halogen reagents, which result in hydrogen evolution, are described.

Synthesis, reactivity, and photochemistry of heterobimetallic rhodium-gold halide and hydride complexes

240th National Meeting (2010)

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