Thermodynamic hydricity is the free energy required for heterolytic cleavage of a metal hydride bond. Experimental thermochemical measurements in water can be challenging and time consuming, motivating efforts to develop simple, straightforward computational methods to calculate reduction potentials, pKa values, and hydricity values of metal hydrides. DFT methods are used to calculate aqueous hydricity values through the individual calculation of reduction potentials and pKa values. The study focuses on structurally homologous iridium hydrides with recently reported experimental hydricity values, which provide direct comparisons with computation. Through the development of appropriate training sets for aqueous reduction potentials and pKa values, accurate computational models have been optimized. Combining these thermodynamic parameters provides aqueous hydricity values that show good numerical agreement with experimental values and also correctly predict the trend of shifting hydricity upon electronic perturbations of the ligand. Our computational model was tested on a training set of molecules to see if there is a systematic error that needs to be fixed with a linear function or a constant error that can be corrected by using a scalar value.

Hydricity calculation of catalysts using DFT methods

253rd National Meeting (2017)

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