Journal
CHEMSUSCHEM
Volume 14, Issue 5, Pages 1308-1315Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.202002718
Keywords
carbon dioxide; electrocatalysis; electrostatic interactions; iron porphyrin; second coordination sphere
Funding
- French National Research Agency [ANR-19-CE05-0020-02]
- CNRS
- CEA Saclay
- LABEX CHARMMMAT
- ICMMO
- University Paris-Saclay
- Ecole Doctorale 2MIB
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Warshel demonstrated the significant role of electrostatic interactions in enzyme catalysis. The use of cationic imidazolium groups in iron porphyrin catalysts enhanced catalytic properties through stabilizing intermediates. Through-space electrostatic interactions were found to outperform through-structure electronic effects in improving catalytic performance.
In his pioneering work to unravel the catalytic power of enzymes, Warshel has pertinently validated that electrostatic interactions play a major role in the activation of substrates. Implementing such chemical artifice in molecular catalysts may help improve their catalytic properties. In this study, a series of tetra-, di-, and mono-substituted iron porphyrins with cationic imidazolium groups were designed. Their presence in the second coordination sphere helped stabilize the [Fe-CO2] intermediate through electrostatic interactions. It was found herein that the electrocatalytic overpotential is a function of the number of embarked imidazolium. Importantly, a gain of six orders of magnitude in turnover frequencies was observed going from a tetra- to a mono-substituted catalyst. Furthermore, the comparative study showed that catalytic performances trend of through-space electrostatic interaction, a first topological effect reported for iron porphyrins, outperforms the classical through-structure electronic effect.
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