The zinc anilide complex 1 was synthesized in one-pot by the stepwise reaction of ZnCl2, with the lithiated ligand and LiNHPh. The family of terminal, primary zinc-anilide complexes has only a couple of structurally characterized examples, and the reactivity of these species has not been investigated in any detail. 1 was proposed to react with H2. An NMR scale reaction of 1 with H2 (1 bar) in C6D6 at 100 °C however yielded only <1% of aniline and the known zinc hydride 2. The equilibrium is displaced almost entirely toward the starting materials. Repeating this experiment in the presence of a suitable trapping agent for 2 led to unambiguous evidence of dihydrogen activation at zinc. Hence, the reaction of 1, H2 and diphenylacetylene after 18 h at 100 °C formed the zinc vinyl complex 3a in low but non-negligible yield of 10%, again the mass balance is unreacted starting materials. In separate experiments, 2 reacted cleanly with diphenylacetylene at 80 °C over 20 h to form 3a in near quantitative yield. These results demonstrate slow dihydrogen activation by 1 and the hydrozincation of an alkyne with the resultant zinc hydride 2 (Scheme 1). Scheme 1. Stoichiometric reactions of 1 with H2 and diphenylacetylene.