Proton transfer kinetics of transition metal hydride complexes and implications for fuel-forming reactions

• Published in: Chemical Society reviews 2023-10, Vol.52 (2), p.7137-7169
• Main Authors: Montgomery, Charlotte L, Amtawong, Jaruwan, Jordan, Aldo M, Kurtz, Daniel A, Dempsey, Jillian L
• Format: Article
• Language: English
• Subjects: Fuels; Kinetics; Metal hydrides; Protons; Rate constants; Transition metals
• ISSN: 0306-0012; 1460-4744
• DOI: 10.1039/d3cs00355h

Proton transfer reactions involving transition metal hydride complexes are prevalent in a number of catalytic fuel-forming reactions, where the proton transfer kinetics to or from the metal center can have significant impacts on the efficiency, selectivity, and stability associated with the catalytic cycle. This review correlates the often slow proton transfer rate constants of transition metal hydride complexes to their electronic and structural descriptors and provides perspective on how to exploit these parameters to control proton transfer kinetics to and from the metal center. A toolbox of techniques for experimental determination of proton transfer rate constants is discussed, and case studies where proton transfer rate constant determination informs fuel-forming reactions are highlighted. Opportunities for extending proton transfer kinetic measurements to additional systems are presented, and the importance of synergizing the thermodynamics and kinetics of proton transfer involving transition metal hydride complexes is emphasized. This review discusses proton transfer kinetics for reactions involving transition metal hydride complexes, highlighting the techniques used to measure proton transfer rate constants and the implications for fuel-forming reactions.