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

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.