Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag 6 H 4 (dppm) 4 (OAc) 2 ] and [Cu 3 H(dppm) 3 (OAc) 2 ].

The group 11 hydride clusters [Ag6 H4 (dppm)4 (OAc)2 ] (1) and [Cu3 H(dppm)3 (OAc)2 ] (2) (dppm = 1,1-bis(diphenylphosphino)methane) were synthesized in moderate yields from the reaction of M(OAc) (M = Ag, Cu) with Ph2 SiH2 , in the presence of dppm. Complex 1 is the first structurally characterized homometallic polyhydrido silver cluster to be isolated. Both 1 and 2 catalyze the hydrosilylation of (α,β-unsaturated) ketones. Notably, this represents the first example of hydrosilylation with an authentic silver hydride complex.