Thermodynamic Hydricity of Transition Metal Hydrides

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• 作者：Eric S. Wiedner ; Matthew B. Chambers ; Catherine L. Pitman ; R. Morris Bullock ; Alexander J. M. Miller ; Aaron M. Appel
• 刊名：Chemical Reviews
• 出版年：2016
• 出版时间：August 10, 2016
• 年：2016
• 卷：116
• 期：15
• 页码：8655-8692
• 全文大小：2030K
• 年卷期：0
• ISSN：1520-6890

文摘

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 H₂ heterolysis method involves measuring the equilibrium of heterolytic cleavage of H₂ 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.