Activations of all Bonds to Silicon (Si-H, Si-C) in a Silane with Extrusion of [CoSiCo] Silicide Cores.

The [BP ]Co(I) synthon Na(THF){[BP ]CoI} (1, [BP ] = κ-PhB(CHP Pr)) reacts with PhSiH or SiH to form unusual {[BP ](SiHR)CoH}═Si═{HCo[BP ]} species (R = Ph, 2a; R = H, 2b; [BP ] = κ-PhB(CHP Pr)) that result from activation of all Si-H and Si-C bonds in the starting silanes. Solution-spectroscopic data (multinuclear NMR, IR) for 2a,b, and the solid-state structure of 2a, indicate substantial Co═Si═Co multiple bonding and minimal interaction of the core Si atom with nearby hydride ligands. In the presence of 4-dimethylaminopyridine (DMAP), 1 reacts with PhSiH to give [BP ](H)CoSiHPh(DMAP) (3). Complexes 2a,b eliminate RSiH upon thermolysis in the presence of DMAP to generate {[BP ]Co(NCHNMe)}═Si═{HCo[BP ]} (4).