Structure and reactivity of a methyl zinc bis(iminophosphorano)methanide chelate complex

Reduction of dimethyl zinc with bis-{trime thylsilyliminodi(phenyl)phosphorano}methane, H2C(Ph2P=NSiMe3)(2) (1), in tobuene gave the alkyl zinc complex [ZrMe{HC(Ph2P=NSiMe3)(2)-kappa(2)N,N'}] (2) via elimination of methane. The crystal structure of the complex confirms its monomeric nature and the bidentate coordination. of the bis(iminophosphorano)methanide ligand to the zinc. AdNCO (Ad = adamantyl) reacted smoothly with 2 via a nucleophilic addition forming a new C-C bond in the novel tripodal alkyl zinc complex [ZnMe{HC{C(O)N(Ad)}(Ph2P=NSiMe3)(2)-kappa(3)N,N',N "}]. 3. The methine carbon atom resonances (delta 28.4 for 2 and 52.9 for 3) were observed as triplets due to the coupling to two equivalent phosphorus atoms. The crystal structure of 3 shows a propeller type arrangement with the three nitrogen atoms of the monoanionic tridentate ligand bound to zinc.