Molecular transition metal hydrides are essential intermediates in a variety of catalytic reactions. Thermodynamic study of metal hydride reactivity provides a framework for tailored catalysts in aqueous hydrogen production and selective hydrogenation of organic substrates. The addition of pendant Lewis acids or bases in the secondary coordination sphere further enhances catalytic activity by minimizing transition state barriers, improving the rate of catalysis. Catalysts for both reactions will discussed with an emphasis on replacing precious metal catalysts with abundant metal congeners. 1) Hydrogen Production. This approach has led to water soluble electrocatalysts for hydrogen production. Thermodynamic considerations are being utilized to optimize activity for specific pH ranges. 2) Hydrogenation Activity. A nickel complex designed for favorable intramolecular heterolytic cleavage of hydrogen catalytically hydrogenates alkynes under ambient conditions. This approach utilizes a bi-functional ligand, and further improvements to develop hydrogenation catalysts for more difficult substrates will be discussed.

Utilizing thermodynamic considerations in the design of molecular transition metal catalysts for hydrogenation activity and aqueous hydrogen production

247th National Meeting (2014)

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