Semi-bridging σ-silyls as Z-type ligands

Abstract

The reactions of SiHPh(NCH₂PPh₂)₂C₆H₄-1,2 with a range of zerovalent group 10 reagents afford the homoleptic bimetallic complexes [M₂{μ-κ³-Si,P,P′-SiPh(CH₂PPh₂)₂C₆H₄}₂] (M = Ni, Pd, Pt) in which the M–M bond is unsymmetrically bridged by two σ-silyl groups. The asymmetry of the M₂Si₂ core increases from Ni through Pd to Pt and is consistent with a bonding description in which one metal acts as an electron pair donor to a trigonal bipyramidal ‘Z-type’ silicon centre, reminsicent of semi-bridging coordination by CO, carbynes and boryl ligands.