Mechanistic Classification of Multicatalysis
4 affiliations
- 1Department of Chemistry
- 2Stockholm University
- 3Department of Chemistry, Stockholm University
- 4Wallenberg Initiative Materials Science for Sustainability
Abstract
Multicatalysis combines two or more catalytic functions within a single reaction network and can unlock reactivity, selectivity, and synthetic efficiency that are difficult to achieve with an individual catalyst. Its mechanistic description, however, remains fragmented across partially overlapping terms such as tandem, relay, cooperative, synergistic, double-activation, and bifunctional catalysis, among others. Here, we propose a mechanism-first classification based on the relationship between catalytic functions and, specifically, on the catalytic ‘currency’ exchanged between them. When the currency is substrate-derived, the coupling is classified as tandem, cooperative, or double activation. When the exchanged currency controls catalyst state rather than contributing to the substrate framework (e.g. electrons, cofactors), the relationship is gated or regenerative, distinguished by whether activation is required only once or repeatedly during turnover. Importantly, the classification is additive, so complex reaction networks are represented as combinations of pairwise relationships. Representative reactions illustrate how this framework resolves mechanistic distinctions that are hidden by conventional labels. By linking nomenclature to the elementary connection between catalytic functions, the classification provides a compact language for comparing multicatalytic systems and a basis for more deliberate catalyst and reaction-network design.
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BibTeX
@misc{riverocrespo2026mechanistic,
title = {{Mechanistic Classification of Multicatalysis}},
author = {Miguel A. Rivero-Crespo},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010289/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010289/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Mechanistic Classification of Multicatalysis
AU - Miguel A. Rivero-Crespo
PY - 2026
DA - 2026/10/12
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010289/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010289/v1
AB - Multicatalysis combines two or more catalytic functions within a single reaction network and can unlock reactivity, selectivity, and synthetic efficiency that are difficult to achieve with an individual catalyst. Its mechanistic description, however, remains fragmented across partially overlapping terms such as tandem, relay, cooperative, synergistic, double-activation, and bifunctional catalysis, among others. Here, we propose a mechanism-first classification based on the relationship between catalytic functions and, specifically, on the catalytic ‘currency’ exchanged between them. When the currency is substrate-derived, the coupling is classified as tandem, cooperative, or double activation. When the exchanged currency controls catalyst state rather than contributing to the substrate framework (e.g. electrons, cofactors), the relationship is gated or regenerative, distinguished by whether activation is required only once or repeatedly during turnover. Importantly, the classification is additive, so complex reaction networks are represented as combinations of pairwise relationships. Representative reactions illustrate how this framework resolves mechanistic distinctions that are hidden by conventional labels. By linking nomenclature to the elementary connection between catalytic functions, the classification provides a compact language for comparing multicatalytic systems and a basis for more deliberate catalyst and reaction-network design.
ER -