Diplatinum Complexes with Bridging Silyl Ligands. Si−H Bond Activation of μ-Silyl Ligand Leading to a New Platinum Complex with Bridging Silylene and Silane Ligands

Abstract

A diplatinum complex with bridging diethylsilyl ligands, [{Pt(PCy3)}2(μ-η2-HSiEt2)2] (1), reacted with an excess of H2SiPh2 to yield [{Pt(PCy3)}2(μ-η2-HSiPh2)2] (2) via exchange of the bridging SiHEt2 ligands with SiHPh2 groups. An equimolar reaction of H2SiPh2 with 1 afforded a mixture of the dinuclear complexes [{Pt(PCy3)}2(μ-η2-HSiEt2)(μ-η2-HSiPh2)] (3) and [{Pt(PCy3)}2(μ-η2:η2-H2SiEt2)(μ-SiPh2)] (4). X-ray crystallographic structure determination of 4 showed bridging coordination of the H2SiEt2 ligand to two Pt centers via two Pt−H−Si three-center two-electron bonds (Pt−Si = 2.375(8) and 2.39(1) Å).