title: 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.
authors.affiliation: Department of Chemistry, University of North Carolina , Chapel Hill, North Carolina 27599, United States.
authors.forename: Kelsey R
authors.identifier: 0000-0003-4189-7064
authors.initials: KR
authors.lastname: Brereton
authors.affiliation: Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.
authors.forename: Sarina M
authors.initials: SM
authors.lastname: Bellows
authors.affiliation: Department of Chemistry and CASCaM, University of North Texas , Denton, Texas 76203, United States.
authors.forename: Hengameh
authors.initials: H
authors.lastname: Fallah
authors.affiliation: Department of Chemistry and CASCaM, University of North Texas , Denton, Texas 76203, United States.
authors.forename: Antonio A
authors.initials: AA
authors.lastname: Lopez
authors.affiliation: Department of Chemistry and CASCaM, University of North Texas , Denton, Texas 76203, United States.
authors.forename: Robert M
authors.initials: RM
authors.lastname: Adams
authors.affiliation: Department of Chemistry, University of North Carolina , Chapel Hill, North Carolina 27599, United States.
authors.forename: Alexander J M
authors.identifier: 0000-0001-9390-3951
authors.initials: AJ
authors.lastname: Miller
authors.affiliation: Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.
authors.forename: William D
authors.identifier: 0000-0003-1932-0963
authors.initials: WD
authors.lastname: Jones
authors.affiliation: Department of Chemistry and CASCaM, University of North Texas , Denton, Texas 76203, United States.
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Cundari