Aqueous Hydricity from Calculations of Reduction Potential and Acidity in Water

作者：Brereton Kelsey R; Bellows Sarina M; Fallah Hengameh; Lopez Antonio A; Adams Robert M; Miller Alexander J M^*; Jones William D^*; Cundari Thomas R^*

来源：Journal of Physical Chemistry B, 2016, 120(50): 12911-12919.

DOI：10.1021/acs.jpcb.6b09864

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 degrees), 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.

• 出版日期2016-12-22