Products Cited in Publications Worldwide The Impact of Electron Donating and Withdrawing Groups on Electrochemical Hydrogenolysis and Hydrogenation of Carbonyl Compounds

The Impact of Electron Donating and Withdrawing Groups on Electrochemical Hydrogenolysis and Hydrogenation of Carbonyl Compounds

Jonah B. Eisenberg; Kwanpyung Lee; Xin Yuan; J. R. Schmidt; Kyoung-Shin Choi

DOI: PMID:

Abstract

The hydrogenolysis or hydrodeoxygenation of a carbonyl group, where the C═O group is converted to a CH2 group, is of significant interest in a variety of fields. A challenge in electrochemically achieving hydrogenolysis of a carbonyl group with high selectivity is that electrochemical of a carbonyl group, which converts the C═O group to an alcohol group (CH-OH), is demonstrated not to be the initial step of hydrogenolysis. Instead, and hydrogenolysis occur in parallel, and they are competing reactions. This means that although both hydrogenolysis and require adding H atoms to the carbonyl group, they involve different intermediates formed on the electrode surface. Thus, revealing the difference in intermediates, transition states, and kinetic barriers for hydrogenolysis and pathways is the key to understanding and controlling hydrogenolysis/hydrogenation selectivity of carbonyl compounds. In this study, we aimed to identify features of reactant molecules that can affect their hydrogenolysis/hydrogenation selectivity on a Zn electrode that was previously shown to promote hydrogenolysis over . In particular, we examined the electrochemical of para-substituted compounds with substituent groups having different electron donating/withdrawing abilities. Our results show a strikingly systematic impact of the substituent group where a stronger electron-donating group promotes hydrogenolysis and a stronger electron-withdrawing group promotes . These experimental results are presented with computational results explaining the substituent effects on the thermodynamics and kinetics of electrochemical hydrogenolysis and pathways, which also provide critically needed information and insights into the transition states involved with these pathways.

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4-(Hydroxymethyl)benzonitrile

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