A Pseudodearomatized PN³P*Ni–H Complex as a Ligand and σ‑Nucleophilic Catalyst

In contrast to the conventional strategy of modifying the reactivities and selectivities of the transition metal and organocatalysts by varying the steric and electronic properties of organic substituent groups, we hereby demonstrate a novel approach that the sigma (σ) nucleophilicity of the imine arm can be significantly enhanced in a pseudodearomatized PN³P* pincer ligand platform to reach unprecedented N-heterocyclic carbene-like reactivity. Accordingly, the imine arm of the PN³P*Ni–H pincer complex efficiently catalyzes the hydrosilylation of aldehydes, cycloaddition of carbon dioxide (CO₂) to epoxides, and serves as a ligand in the Ru-catalyzed dehydrogenative acylation of amines with alcohols.