Silyl and germyl compounds of platinum and palladium. Part I. Platinum derivatives of monosilane and monogermane

Abstract

Reactions of trans-XP(PEt₃)₂H with MH_4–nX_n(M = Si or Ge; X = Cl, Br, I; n= 0–3) in benzene at room temperature give trans-XPt(PEt₃)₂MH_3–nX_n; with MH₃Y (Y = F, Cl, Br, I) halogen exchange leads to the formation of that product in which the heavier halogen is bound to Pt. Oxidative addition of MH₃X to trans-(Et₃P)₂Ptl₂ gives (Et₃P)₂Pt(MH₂X)(H)I₂, which slowly decomposes at room temperature to give H₂ and trans-IPt(PEt₃)₂MHXI. Reaction of MH₄ or of MH₃Cl with trans-(Et₃P)₂PtCl₂ is much slower and no product containing 6-coordinate Pt was detected. The mechanisms of these reactions and of the reactions of trans-CIPt(PEt₃)₂MH₂Cl with hydrogen chloride are discussed; vibrational and ¹H n.m.r. spectra of the platinum complexes are described. Reactions of trans-CIPt(PEt₃)₂SiH₂Cl with methanol and with water are complicated; with dimethylamine, trans-CIPt(PEt₃)₂SiH₂NMe₂ is formed. Reactions of trans-CIPt(PEt₃)₂SiH₂Cl with Et₃P, with Me₃N, with PH₃, with Mel, with hexene, and with ethylene have been investigated.