Eco-friendly zinc dihydrides stabilized by N-heterocyclic carbenes were demonstrated to be highly efficient catalysts for the double hydroboration of nitriles with pinacolborane, exhibiting turnover frequencies up to 3000 h−1 at room temperature under solvent-free conditions. The reactions afforded corresponding diboronated amines with excellent yields and good functional group tolerance. A single Zn–H insertion product was isolated from a stoichiometric reaction of zinc dihydride with nitrile, and was proved to be an active species in this transformation. Kinetic studies were performed to give some insights into the catalytic reactions. In addition, zinc dihydride species also showed high activity for the hydroboration of imines to boronated amines.
