Transition metal hydrides are reactive intermediates in a wide variety of catalytic reactions. Thermodynamic characterization of their reactivity has been instrumental in developing new catalysts with improved activity that can operate under milder conditions. Extensive studies of the thermodynamic properties of metal bis(diphosphine) complexes have elucidated the electronic and steric effects underlying their reactions of these complexes with H2 and the proton and hydride donor abilities of the resulting metal hydrides. However, similar data for analogous mixed-ligand complexes containing one triphosphine and one monophosphine ligand have not been reported. This presentation will present the results from a combination of computational and experimental studies of the hydricities and acidities of metal(triphosphine)(monophosphine) complexes from Groups 9 and 10. Studies using a variety of phosphine ligands address the electronic and steric factors underlying their reactivity, with important implications for their use as catalysts in CO2 reduction and H2 electrocatalysis.

Thermodynamic studies of metal-hydride bonding with a mixed triphosphine/monophosphine ligand set

ACS Spring Meeting 2021

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