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

Handford RC , Smith PW , Tilley TD
Journal of the American Chemical Society
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]Co(H)=SiHPh(DMAP) (3). Complexes 2a,b eliminate RSiH upon thermolysis in the presence of DMAP to generate {[BP]Co(NCHNMe)}=Si={HCo[BP]} (4).

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