Aqueous Hydricity from Calculations of Reduction Potential and Acidity in Water.

Abstract

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 (pKa), 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.