Bis(phosphinimino)methanides as non-innocent ligand in zinc chemistry: synthesis and structures

Abstract

Reactions of the bis(phosphinimino)methane {CH₂(Ph₂PNSiMe₃)₂} with the zinc dihalides ZnCl₂ and ZnI₂ afforded the corresponding bis(phosphinimino)methane complexes [{(Me₃SiNPPh₂)₂CH₂}ZnCl₂] (1) and [{(Me₃SiNPPh₂)₂CH₂}ZnI₂] (2). In contrast, treatment of {CH₂(Ph₂PNSiMe₃)₂} with ZnPh₂ in toluene gave the bis(phosphinimino)methanide complex of [{(Me₃SiNPPh₂)₂CH}ZnPh] (3). Further reaction of 3 with the heterocumulenes di(p-tolyl)carbodiimine and diphenyl ketene resulted via a nucleophilic addition of the methine carbon atom of the {CH(Ph₂PNSiMe₃)₂}⁻ ligand to the heterocumulenes in a C–C bond formation. New tripodal phenyl zinc complexes of composition [{(Me₃SiNPPh₂)₂CH)(p-Tol)NC–N(p-Tol)}ZnPh] (4) and [{(Me₃SiNPPh₂)₂CH)(Ph₂CC–O)}ZnPh] (5) were obtained.