Issue 22, 2020

Thermodynamic and kinetic hydricity of transition metal hydrides

Abstract

The prevalence of transition metal-mediated hydride transfer reactions in chemical synthesis, catalysis, and biology has inspired the development of methods for characterizing the reactivity of transition metal hydride complexes. Thermodynamic hydricity represents the free energy required for heterolytic cleavage of the metal–hydride bond to release a free hydride ion, H, as determined through equilibrium measurements and thermochemical cycles. Kinetic hydricity represents the rate of hydride transfer from one species to another, as measured through kinetic analysis. This tutorial review describes the common methods for experimental and computational determination of thermodynamic and kinetic hydricity, including advice on best practices and precautions to help avoid pitfalls. The influence of solvation on hydricity is emphasized, including opportunities and challenges arising from comparisons across several different solvents. Connections between thermodynamic and kinetic hydricity are discussed, and opportunities for utilizing these connections to rationally improve catalytic processes involving hydride transfer are highlighted.

Graphical abstract: Thermodynamic and kinetic hydricity of transition metal hydrides

Supplementary files

Article information

Article type
Tutorial Review
Submitted
20 Dzi 2020
First published
11 Mha 2020

Chem. Soc. Rev., 2020,49, 7929-7948

Author version available

Thermodynamic and kinetic hydricity of transition metal hydrides

K. R. Brereton, N. E. Smith, N. Hazari and A. J. M. Miller, Chem. Soc. Rev., 2020, 49, 7929 DOI: 10.1039/D0CS00405G

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