Homoleptic nickel and rhodium diphosphine complexes, both with pendant amines (so-called P2N2 ligands) and without have been thoroughly studied for hydrogen activation chemistry. Using these systems as inspiration, we have developed homoleptic rhodium P2N2 complexes that generate powerful hydride species of sufficient strength to reduce carbon dioxide to formate. Structural, electrochemical , and thermodynamic measurements will be presented, along with hydrogen activation and catalytic carbon dioxide hydrogenation studies. We have also synthesized mixed-ligand bis-diphosphine bis-N-heterocyclic carbene nickel(II) systems which display unusual two-electron redox behavior and reduction potentials that are similar to the aforementioned rhodium complexes. Results of synthetic, structural, and electrochemical studies of these compounds will be presented, as well studies of the hydrides of these compounds, their hydrogen activation activity, and work towards adapting these new ligand scaffolds for nickel-based carbon dioxide hydrogenation catalysts.

Carbon dioxide hydrogenation by late transition metal phosphine and N-heterocyclic carbene complexes

251st National Meeting (2016)

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