The group 11 hydride clusters [Ag6H4(dppm)(4)(OAc)(2)] (1) and [Cu3H(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 Ph2SiH2, 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 (alpha/beta-unsaturated) ketones. Notably, this represents the first example of hydrosilylation with an authentic silver hydride complex.