The development of molecular catalysts for small molecule reduction is a longstanding goal with increasing importance as a strategy for chemical energy storage and conversion. This presentation will describe studies of new metal-phosphine complexes designed to facilitate small molecule reduction by mediating proton and hydride transfer within the primary and secondary coordination spheres. These complexes use Group 9 or 10 transition metals with a mixed triphosphine and monophosphine ligand set, in which the monophosphine contains an embedded organic hydride donor. Studies of the stoichiometric and catalytic reactivity of these complexes towards small molecules such as H2 and CO2 will be presented. The reaction conditions can be controlled such that H2 activation selectively generates ligand-based or metal-based hydrides, and these two types of hydrides show differing reactivities towards substrates such as CO2. In addition, studies of the thermodynamic hydride and proton donor abilities of these complexes will be presented. The mixed triphosphine/monophosphine donor set shows interesting structural and electronic differences with the well studied metal bis(diphosphine) analogues that are known to be effective catalysts for CO2 hydrogenation and H2 oxidation.

Metal-phosphine complexes with embedded organic hydride donors: hydrides in the primary and secondary coordination spheres

ACS Spring Meeting 2021

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