Thermodynamic hydricity has been previously used to design molecular catalysts for H2 oxidation and production, CO2 reduction, and formate oxidation. This talk will describe recent efforts from our group to apply the hydricity parameter to the catalytic hydrogenation of a wide range of carbonyl compounds, including ketones and esters. Hydrogenation of the carbonyl moiety may undergo three distinct chemical routes: a stepwise hydride transfer/proton transfer, a stepwise proton transfer/hydride transfer, and a concerted proton/hydride transfer. Herein we study the complex HRh(dmpe)2, which is known to be a very strong hydride donor. By matching the hydricity value of HRh(dmpe)2 to the relative hydride affinities of a range of carbonyl substrates, a predictive correlation can be formed to determine the favorability of hydride transfer for a variety of substituted carbonyl reduction reactions. The substrate dependence, along with spectroscopic and crystallographic evidence, suggests this catalyst operates by stepwise hydride transfer/proton transfer.

Thermodynamic hydricity as a tool for designing catalysts for hydrogenation of ketones and esters

2019 Fall National Meeting

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