An emerging strategy in developing catalysts for reactions involving activation and utilization of H2 is to incorporate reactive functionalities into their secondary coordination spheres. These reactive groups are often capable of mediating proton or hydride movement. This presentation will describe the preparation of trifunctional nickel complexes containing both a proton relay and an organic hydride donor. These complexes contain a tridentate PNP phosphine ligand with a basic amine and a monodentate phosphine ligand containing an embedded hydride donor. Proton transfer from a nickel hydride species to the amine and hydride transfer to the organic phenanthridinium group are described and compared to the reactivity of monofunctional nickel(triphosphine)(monophosphine) complexes. The implications for catalytic reactions will be discussed.

Trifunctional nickel complexes containing ligand-based acidic and hydridic groups

ACS Spring 2022

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