Unusual mechanism of paramagnetic nickel-catalysed α-alkylation of amides

Nickel transition-metal catalysts are important materials which are widely used in (de)hydrogenation reactions. Typical NiII catalysts adopt a square planar geometry and a low-spin state owing to their d8 electronic configuration. Here, we describe a mechanistic investigation of a novel octahedral NiII catalyst with a paramagnetic nature catalysing the α-alkylation of amides. Both non-bifunctional and bifunctional pathways were considered. In addition, we clarified the superiority of the high-spin state by comparing the geometries, valence electronic configurations, and rate-limiting energy barriers of the high- and low-spin states. Our results indicate that the novel octahedral nickel catalyst favours the bifunctional pathway and tends to maintain a high-spin state throughout the reaction due to the N-arm ligand. This computational study suggests that the spin state has the potential to influence the catalyst structure and reaction mechanism. Furthermore, these findings present novel insights for the design of NiII catalysts with high-spin states.