The reaction of an equimolar mixture of N, N′-bis(2-pyridylmethyl)acetamidine ( 1) and di(tert-butyl)phosphane with dimethylzinc yields dinuclear bis(methylzinc) bis(2-pyridylmethyl)acetamidinate di(tert-butyl)phosphanide ( 2). A similar protocol allows the preparation of bis(alkylzinc) bis(2-pyridylmethyl)acetamidinate tert-butylamide [zinc-bound methyl ( 3) or trimethylsilylmethyl group ( 4)]. The reactions of 3 and 4 with diphenylsilane lead to the formation of insoluble dimeric bis(alkylzinc) N, N′-bis(2-pyridylmethyl)acetamidinate hydrides [zinc-bound methyl ( 5) or trimethylsilylmethyl group ( 6)]. These zinc hydrides decompose once dissolved under formation of elemental zinc thus hampering catalytic applications. Molecular structures of [( 1)ZnCl 2] as well as of the zinc complexes 2 to 6 are discussed.