Thermodynamic and kinetic hydricity of transition metal hydrides
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 hetero...
Saved in:
| Published in | Chemical Society reviews Vol. 49; no. 22; pp. 7929 - 7948 |
|---|---|
| Main Authors | , , , |
| Format | Journal Article |
| Language | English |
| Published |
London
Royal Society of Chemistry
16.11.2020
Royal Society of Chemistry (RSC) |
| Subjects | |
| Online Access | Get full text |
| ISSN | 0306-0012 1460-4744 1460-4744 |
| DOI | 10.1039/d0cs00405g |
Cover
| Summary: | 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.
This review of thermodynamic and kinetic hydricity provides conceptual overviews, tutorials on how to determine hydricity both experimentally and computationally, and salient case studies. |
|---|---|
| Bibliography: | Kelsey Brereton obtained her BS from Pepperdine University in 2013 and received a PhD from The University of North Carolina at Chapel Hill while working with Professor Alexander Miller. Upon completion of her doctoral program, Kelsey returned to Pepperdine University to join the faculty as a Visiting Professor of Chemistry where her research with undergraduate students focuses on inorganic and computational chemistry. Nilay Hazari is currently a Professor of Chemistry at Yale University. As part of his scientific training, he completed his undergraduate degree at the University of Sydney (under the supervision of Professor Leslie Field), his PhD at Oxford University (under the supervision of Professor Jennifer Green), and a postdoctoral position at Caltech (under the supervision of Professors John Bercaw and Jay Labinger). His group is interested in understanding the mechanisms by which transition metal complexes react with substrates that are relevant to both energy applications and the synthesis of pharmaceuticals. 10.1039/d0cs00405g Alexander Miller is an Associate Professor of Chemistry at the University of North Carolina at Chapel Hill (UNC). He obtained his BS at the University of Chicago in 2005 (working with Prof. Greg Hillhouse), and his PhD at the California Institute of Technology in 2011 (working with Profs. John Bercaw and Jay Labinger). After a postdoctoral fellowship at the University of Washington, Seattle working with Profs. Karen Goldberg and James Mayer, Alex joined the faculty at UNC in 2012. His research group takes a mechanism-guided approach to the design and discovery of catalysts for sustainable chemical and fuel synthesis. Nicholas Smith obtained his BS from the University of Minnesota-Twin Cities in 2015. He is currently a PhD student in the laboratory of Professor Nilay Hazari in the Department of Chemistry at Yale University. His current research is focused on addressing the challenges of using base-metal pincer complexes for (de)hydrogenative reactions and their applications in the area of energy storage. Electronic supplementary information (ESI) available: Thermochemical derivations (PDF). Complete table and charts of thermodynamic hydricity values (XLS). Number-line chart of thermodynamic hydricity in acetonitrile (PDF). Number-line chart of thermodynamic hydricity in water (PDF). See DOI ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23 USDOE Office of Science (SC), Basic Energy Sciences (BES) SC0014255 |
| ISSN: | 0306-0012 1460-4744 1460-4744 |
| DOI: | 10.1039/d0cs00405g |