Issue 24, 2023

Local reactivity descriptors to decipher the electrochemical hydrogenation of unsaturated carboxylic acids

Abstract

The decarbonization of chemical manufacturing is a multifaceted challenge that requires technologies able to selectively convert CO2-sequestering feedstocks using renewable energy. The electrochemical conversion of biomass is well-positioned to address this need. However, the electroactivity of biobased molecules that carry multiple redox centers remains challenging to predict and control. For instance, cis,cis-muconic acid, a conjugated dicarboxylic acid, is electrohydrogenated to trans-3-hexenedioic acid (t3HDA) with excellent yield and stereoselectivity while free energy calculations predict mixtures of 2- and 3-hexenedioic acids. To decipher this discrepancy, we studied the electrohydrogenation of C4 and C6 unsaturated acids, diacids, and their esters, and tied the observed product distributions to the electronic structure of the parent molecules. We show that the electrohydrogenation of the three isomers of muconic acid proceeds through a hydrogenating proton-coupled electron transfer (PCET) in the α position of the carboxylic acids and invariably yields t3HDA as the sole product. The selectivity can be explained by the electron-withdrawing effect of the carboxylic acid groups and the resulting perturbation of the local electron density that promotes the 2,5-hydrogenation over the thermodynamically-preferred 2,3-hydrogenation. This electronic perturbation is reflected in the computed Fukui indices, which can serve as local reactivity descriptors to predict product distributions not captured by calculated reaction thermochemistry. In addition to predicting the electroactivity of other unsaturated acids, this approach can provide insights into homogeneous electrochemical processes that may coexist with surface-mediated electrocatalytic transformations.

Graphical abstract: Local reactivity descriptors to decipher the electrochemical hydrogenation of unsaturated carboxylic acids

Supplementary files

Article information

Article type
Paper
Submitted
05 aug 2023
Accepted
18 sep 2023
First published
20 sep 2023
This article is Open Access
Creative Commons BY-NC license

Green Chem., 2023,25, 10387-10397

Local reactivity descriptors to decipher the electrochemical hydrogenation of unsaturated carboxylic acids

M. N. Dell'Anna, G. Gupta, P. T. Prabhu, T. Chu, L. T. Roling and J. Tessonnier, Green Chem., 2023, 25, 10387 DOI: 10.1039/D3GC02909C

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