Preparation and reactions of some ionic organoplatinum(II) complexes

Abstract

The ionic complexes [Pt(diphos)(PEt₃)R]Cl (R = Me, Et, or Ph; diphos = Ph₂P·CH₂·CH₂·PPh₂) have been prepared by the reaction of diphos with [Pt(Et₃P)₂RCl]. The complexes undergo a thermal reaction leading to [Pt(diphos)RCI] and Et₃P (R = Me or Ph); for R = Et, ethylene loss is the main reaction. The complex [Pt(diphos)(GeMe₃)Cl] has been prepared similarly from [Pt(diphos)(PEt₃)GeMe₃]Cl. Metathetical (Nal or NaBPh₄) and Pt–C bond cleavage (I₂ or HCl) reactions are discussed. Thus iodine and [Pt(diphos)(PEt₃)Me]I rapidly give [Pt(diphos)I₂] and [Et₃PMe]I, whilst HCl and [Pt(diphos)(PEt₃)R]Cl (R = Me or Et) give RH and [Pt(diphos)(PEt₃)CI]CI only slowly. The n.m.r. spectra of the complexes are discussed.