A Rh^II−Au^II Bimetallic Core with a Direct Metal−Metal Bond

The d⁸···d¹⁰ heterobimetallic Rh^IAu^I(tfepma)₂(CN^tBu)₂Cl₂ (1) complex (tfepma = bis[bis(trifluoroethoxy)phosphino]methylamine) is oxidized by KAu^IIICl₄ to give the first structurally characterized d⁷−d⁹ Rh^II−Au^II singly bonded metal complex [Rh^IIAu^II(tfepma)₂(CN^tBu)₂Cl₃]⁺[Au^ICl₂]^- (2). Complex 2 undergoes a thermal intermetal redox reaction to generate fac-Rh^III(tfepma)(CN^tBu)Cl₃ (3) and Au₂^I,I(tfepma)₂Cl₂ (4).