Reactions of R2P–P(SiMe3)Li with [(R′3P)2PtCl2]. A general and efficient entry to phosphanylphosphinidene complexes of platinum. Syntheses and structures of [(η2-PPiPr2)Pt(p-Tol3P)2], [(η2-PPtBu2)Pt(p-Tol3P)2], [{η2-PP(NiPr2)2}Pt(p-Tol3P)2] and [{(Et2PhP)2Pt}2P2]

Abstract

The reactions of lithium derivatives of diphosphanes R₂P–P(SiMe₃)Li (R = ^tBu, ⁱPr, Et₂N and ⁱPr₂N) with [(R′₃P)₂PtCl₂] (R′₃P = Et₃P, Et₂PhP, EtPh₂P and p-Tol₃P) proceed in a facile manner to afford side-on bonded phosphanylphosphinidene complexes of platinum [(η²-PPR₂)Pt(PR′₃)₂]. The related reactions of Ph₂P–P(SiMe₃)Li with [(R′₃P)₂PtCl₂] did not yield [(η²-PPPh₂)Pt(PR′₃)₂] and resulted mainly in the formation of [{(R′₃P)₂Pt}₂P₂], Ph₂P–PLi–PPh₂, (Me₃Si)₂PLi and (Me₃Si)₃P. Crystallographic data are reported for the compounds [(η²-PPR₂)Pt(p-Tol₃P)₂] (R = ^tBu, ⁱPr, (ⁱPr₂N)₂P) and for [{(Et₂PhP)₂Pt}₂P₂].