Lewis Acid-Tethered (cAAC)-Copper Complexes: Reactivity for Hydride Transfer and Catalytic CO2 Hydrogenation.

We present a series of borane-tethered cyclic (alkyl)(amino)carbene (cAAC)-copper complexes, including a borane-capped Cu(I) hydride. This hydride is unusually hydridic and reacts rapidly with both CO2 and 2,6-dimethylphenol at room temperature. Its reactivity is distinct from variants without a tethered borane, and the underlying principles governing the enhanced hydricity were evaluated experimentally and theoretically. These stoichiometric results were extended to catalytic CO2 hydrogenation, and the borane-tethered (intramolecular) system exhibits ~3-fold enhancement relative to an intermolecular system.