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 اپریل 2020
First published
11 اگست 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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements