Modifying Catalytic Sustainability in Renaud Catalysts: Hints From Aromaticity, Conceptual DFT, and Steric Mapping
Abstract
Catalytic hydrogenation is a key transformation in the chemical and pharmaceutical industries, traditionally relying on noblemetal catalysts such as palladium, ruthenium, and iridium. However, the scarcity, high cost, and environmental concerns associated with these metals have motivated the search for sustainable alternatives based on abundant first-row transition metals. Among them, Knölker-type iron complexes have emerged as promising candidates for efficient hydrogenation catalysis. This predictive study investigates how structural modifications of the cyclopentadienone ligand of the Renaud ligand and annulated-ring framework affect the catalytic activity of iron-based hydrogenation catalysts. Particular attention is devoted to the catalyst activation process and the rate-determining hydrogenation step. Catalyst activation occurs through CO ligand dissociation promoted by trimethylamine-N-oxide, generating the active iron species. The hydrogenation step, involving molecular hydrogen transfer, represents the highest energetic barrier in the catalytic cycle, although protic solvents such as ethanol or water can facilitate this process. The computational results demonstrate that appropriate substituent and ring modifications substantially lower the activation barriers, leading to improved catalytic efficiency. Parameterization by different techniques was performed to understand reactivity trends and interaction patterns.
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BibTeX
@article{alcaide2026modifying,
title = {{Modifying Catalytic Sustainability in Renaud Catalysts: Hints From Aromaticity, Conceptual DFT, and Steric Mapping}},
author = {Carles Alcaide and Clara Mauclaire and Muhammad Ehtisham and Sílvia Simon and Sylvain Gaillard and Jean Luc Renaud and Albert Poater},
journal = {European Journal of Organic Chemistry},
year = {2026},
month = sep,
doi = {10.1002/ejoc.70845},
url = {https://normandie-univ.hal.science/hal-05781015v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Modifying Catalytic Sustainability in Renaud Catalysts: Hints From Aromaticity, Conceptual DFT, and Steric Mapping
AU - Carles Alcaide
AU - Clara Mauclaire
AU - Muhammad Ehtisham
AU - Sílvia Simon
AU - Sylvain Gaillard
AU - Jean Luc Renaud
AU - Albert Poater
PY - 2026
DA - 2026/09/30
JO - European Journal of Organic Chemistry
DO - 10.1002/ejoc.70845
UR - https://normandie-univ.hal.science/hal-05781015v1
AB - Catalytic hydrogenation is a key transformation in the chemical and pharmaceutical industries, traditionally relying on noblemetal catalysts such as palladium, ruthenium, and iridium. However, the scarcity, high cost, and environmental concerns associated with these metals have motivated the search for sustainable alternatives based on abundant first-row transition metals. Among them, Knölker-type iron complexes have emerged as promising candidates for efficient hydrogenation catalysis. This predictive study investigates how structural modifications of the cyclopentadienone ligand of the Renaud ligand and annulated-ring framework affect the catalytic activity of iron-based hydrogenation catalysts. Particular attention is devoted to the catalyst activation process and the rate-determining hydrogenation step. Catalyst activation occurs through CO ligand dissociation promoted by trimethylamine-N-oxide, generating the active iron species. The hydrogenation step, involving molecular hydrogen transfer, represents the highest energetic barrier in the catalytic cycle, although protic solvents such as ethanol or water can facilitate this process. The computational results demonstrate that appropriate substituent and ring modifications substantially lower the activation barriers, leading to improved catalytic efficiency. Parameterization by different techniques was performed to understand reactivity trends and interaction patterns.
SN - 1434-193X
SN - 1099-0690
ER -