Synthesis and X‐ray Crystal Structures of Zinc Complexes Supported by Chelating Ligands: Various Reactions of α‐Iminopyridines with ZnEt 2

α‐Iminopyridine (α‐IP) is an important redox‐noninnocent ligand. The substituents on the imino function of α‐IPs have important impact on the reaction selectivity with diethylzinc. For the α‐IPs with a hydrogen substituent on the imino carbon, reduction occurred for the non‐bulky N‐substituents phenyl and 2‐methylphenyl groups, whereas alkyl addition and coupling reactions can be selectively achieved for the sterically bulky N ‐substituents 2,6‐dimethylphenyl or 2,4,6‐trimethylphenyl group. However, for the α‐IPs with a CH 3 substituent on the imino carbon, the deprotonation reaction happened regardless of the N ‐substituents of 2‐methylphenyl or 2,6‐dimethylphenyl group. All the products were isolated and characterized by single‐crystal X‐ray diffraction. The possible mechanisms of these reactions were also discussed.