Transition metal hydrides can react as either hydride or proton donors. Tuning their reactivity can have important effects on catalytic activity and selectivity, as has been established for metal bis(diphosphine) complexes with the general formula HM(P2)2. The acidity and hydricity data for this class of complexes has successfully guided the development of catalysts for CO2 hydrogenation and H2 electrocatalysis. Our group has been studying the reactivity of Group 9 and 10 transition metal hydrides with the general formula HM(P3)(P'), combining a tridentate and a monodentate phosphine ligand. This presentation will describe the results from a combination of experimental and computational studies that have determined the acidities and hydricities for a variety of metal and ligand combinations within this framework. The effect on the proton and hydride donor abilities from varying the metal ion, ligand donors, and substituent size will be discussed. The use of this data to identify active catalysts for CO2 hydrogenation will also be presented.

Hydricities and acidities of metal(triphosphine)(monophosphine) hydride complexes

ACS Spring 2022

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