Reactions of the bis(phosphinimino)methane {CH2(Ph 2PNSiMe3)2} with the zinc dihalides ZnCl 2 and ZnI2 afforded the corresponding bis(phosphinimino) methane complexes [{(Me3SiNPPh2)2CH 2}ZnCl2] (1) and [{(Me3SiNPPh2) 2CH2}ZnI2] (2). In contrast, treatment of {CH2(Ph2PNSiMe3)2} with ZnPh 2 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)(Ph 2CC-O)}ZnPh] (5) were obtained. © 2010 The Royal Society of Chemistry.