Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag₆H₄(dppm)₄(OAc)₂] and [Cu₃H(dppm)₃(OAc)₂]

The group 11 hydride clusters [Ag 6 H 4 (dppm) 4 (OAc) 2 ] ( 1 ) and [Cu 3 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 Ph 2 SiH 2, 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.