Silyl and germyl complexes of platinum and palladium. Part 4. Reactions between four-co-ordinated halogenohydridobis(triethylphosphine)platinum(II) complexes and silyl-amines or -phosphines

Abstract

Reactions between NH(SiH₃)₂ and trans-[PtH(I)(PEt₃)₂] give trans-[PtI(PEt₃)₂(H₂SiNHSiH₃)] and trans-[{PtI(PEt₃)₂(SiH₂)}₂NH]; with N(SiH₃)₃, only trans-[PtI(PEt₃)₂{H₂SiN(SiH₃)₂}] is formed, probably for steric reasons. With PH₂(SiH₃) or PH(SiH₃)₂, PH₃ and trans-[PtI(PEt₃)₂(SiH₃)] are produced; P(SiH₃)₃ reacts with a four-fold excess of trans-[PtH(I)(PEt₃)₂] to give PH₃ and trans-[PtI(PEt₃)₂(SiH₃)], but with reacting ratios (phosphine : Pt) between 1 : 1 and 2 : 1 the products are trans-[PtI(PEt₃)₂{H₂SiP(SiH₃)₂}] and trans-[{PtI(PEt₃)₂(SiH₂}₂PSiH₃]. The only silyl compound of this series to give an identifiable species with trans-[PtCl(H)(PEt₃)₂] is PH₂(SiH₃) which produces trans,trans-[PH₂{PtH(PEt₃)₂}₂]⁺. The complexes described have been characterised by ¹H and ³¹P n.m.r. spectroscopy and by heteronuclear double resonance. Most of these reactions are considered to involve derivatives of six-co-ordinate platinum as intermediates.