Aqueous Hydricity from Calculations of Reduction Potential and Acidity in Water

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• 作者：Kelsey R. BreretonSarina M. Bellows ; Hengameh Fallah ; Antonio A. Lopez ; Robert M. Adams ; Alexander J. M. Miller ; William D. JonesThomas R. Cundari
• 刊名：Journal of Physical Chemistry B
• 出版年：2016
• 出版时间：December 22, 2016
• 年：2016
• 卷：120
• 期：50
• 页码：12911-12919
• 全文大小：492K
• ISSN：1520-5207

文摘

Hydricity, or hydride donating ability, is a thermodynamic value that helps define the reactivity of transition metal hydrides. To avoid some of the challenges of experimental hydricity measurements in water, a computational method for the determination of aqueous hydricity values has been developed. With a thermochemical cycle involving deprotonation of the metal hydride (pK_a), 2e^– oxidation of the metal (E°), and 2e^– reduction of the proton, hydricity values are provided along with other valuable thermodynamic information. The impact of empirical corrections (for example, calibrating reduction potentials with 2e^– organic versus 1e^– inorganic potentials) was assessed in the calculation of the reduction potentials, acidities, and hydricities of a series of iridium hydride complexes. Calculated hydricities are consistent with electronic trends and agree well with experimental values.