Structure and Reactivity of a Methyl Zinc Bis(iminophosphorano)methanide Chelate Complex

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Abstract

Reaction of dimethyl zinc with bis{trimethylsilyliminodi(phenyl)phosphorano}methane, H2C(Ph2PNSiMe3)2 (1), in toluene gave the alkyl zinc complex [ZnMe{HC(Ph2PNSiMe3)2-κ2N,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)}(Ph2PNSiMe3)2-κ3N,N‘,N"}], 3. The methine carbon atom resonances (δ 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.

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