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Thermodynamic Hydricity of Transition Metal Hydrides [electronic resource].

Published
Arlington, Va. : National Science Foundation (U.S.), 2016.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description
pages 8,655-8,692 : digital, PDF file
Additional Creators
Pacific Northwest National Laboratory (U.S.), National Science Foundation (U.S.), and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
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 bondbreaking 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 H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa 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. Finally, 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.
Report Numbers
E 1.99:1313998
Subject(s)
Note
Published through SciTech Connect.
08/02/2016.
Chemical Reviews 116 15 ISSN 0009-2665 AM
Eric S. Wiedner; Matthew B. Chambers; Catherine L. Pitman; R. Morris Bullock; Alexander J. M. Miller; Aaron M. Appel.
Funding Information
SC0014255
CHE-1205189
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