Dr. Antoine Simonneau
Small Molecule Activation (SMAc) Research Group
LCC-CNRS, Université de Toulouse, CNRS, Université de Toulouse, 31077 Toulouse, France
antoine.simonneau [at] lcc-toulouse.fr (antoine.simonneau@lcc-toulouse.f)
15h45 – 17h15
Amphi Anne L'Huillier
Activation of small molecules by donor-acceptor systems is conceptually important as many catalytic processes rely on the synergistic action of electron-rich and -poor sites to cooperatively activate and cleave bonds. This pertains to both the biological and industrial chemistry contexts. In this presentation, I will describe hybrid main-group/transition metal dyads initially developed for N2 activation, taking inspiration from the frustrated Lewis pair chemistry[1] and based on low-valent group 6 complexes and highly electron-deficient group 13 Lewis acids.[2–4] Their application to other small molecules will be discussed. Finally, I will introduce some of our recent work on “Frustrated Redox Triads” incorporating Lewis “superacids” and discuss the concept of Lewis Acid-Coupled Electron Transfer (LACET).[5–7]
References
[1] D. W. Stephan, “The broadening reach of frustrated Lewis pair chemistry” Science 2016, 354, aaf7229.
[2] A. Simonneau, R. Turrel, L. Vendier, M. Etienne, “Group 6 Transition-Metal/Boron Frustrated Lewis Pair Templates Activate N2 and Allow its Facile Borylation and Silylation” Angew. Chem. Int. Ed. 2017, 56, 12268–12272.
[3] D. Specklin, M.-C. Boegli, A. Coffinet, L. Escomel, L. Vendier, M. Grellier, A. Simonneau, “An orbitally adapted push–pull template for N2 activation and reduction to diazene-diide” Chem. Sci. 2023, 14, 14262–14270.
[4] L. Escomel, F. F. Martins, L. Vendier, A. Coffinet, N. Queyriaux, V. Krewald, A. Simonneau, “Coordination of Al(C6F5)3 vs. B(C6F5)3 on group 6 end-on dinitrogen complexes: chemical and structural divergences” Chem. Sci. 2024, 15, 11321–11336.
[5] L. Escomel, L. Vendier, D. Gatineau, F. Molton, C. Duboc, M. Gennari, A. Simonneau, “Reductive Cleavage of Dioxygen Mediated by a Lewis Superacidic Bis(borane)” JACS Au 2025, 5, 3032–3038.
[6] L. Escomel, Q. Lepeintre, C. Gonçalves, L. Vendier, S. Bontemps, J. A. Panetier, A. Simonneau, “Reduction of CO2 Beyond Redox Limits Enabled by Lewis Acid-Coupled Electron Transfer” in revision.
[7] S. Fukuzumi, K. Ohkubo, Y.-M. Lee, W. Nam, “Lewis Acid Coupled Electron Transfer of Metal–Oxygen Intermediates” Chem. – Eur. J. 2015, 21, 17548–17559.