Journal
CHEMICAL REVIEWS
Volume 116, Issue 15, Pages 8655-8692Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemrev.6b00168
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences Biosciences
- Center for Molecular Electrocatalysis, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences
- Division of Chemical Sciences, Geosciences AMP
- Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy [DE-SC0014255]
- National Science Foundation Center for Enabling New Technologies [CHE-1205189]
- U.S. Department of Energy (DOE) [DE-SC0014255] Funding Source: U.S. Department of Energy (DOE)
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1205189] Funding Source: National Science Foundation
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Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bond breaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H-). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H-2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H-2 in the presence of a base, and the potential-pK(a) method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen.
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