Density functional theory calculations were used to assess the viability of an Ir(III) complex, Cp*Ir(bpy-(OH)2)(H2O)[OTf]2, as a catalyst for the aldehyde-water shift (AWS) reaction (R-CHO + H2O ? R-COOH + H2), a reaction of considerable interest due to its potential implications for bulk hydrogen production. Calculated thermodynamic and kinetic values for the steps in a proposed reaction mechanism with R = Me are reported. Calculations were conducted in both gas phase and continuum water solvent, with both sets of data showing similar energetic trends. Overall, the data suggest that the Ir(III) complexis a catalyst lead worthy of experimental consideration. Rh(III) and Ru(II) variants of the proposed catalyst were also tested, and the following order of catalyst effectiveness was proposed: Rh > Ir > Ru, suggesting that the Rh variant is also worthy of experimental testing.

DFT modeling of the aldehyde-water shift reaction

247th National Meeting (2014)

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