As one of the outpost of fundamental science at the CIRe team, we intend to discover novel organic functions in order to offer original opportunities to interact with electrons and photons at the molecular level. Our targets are often “impossible” molecules: elusive compounds that are commonly considered as too reactive to be isolated, or even to be observed. We stabilize these them through rational modifications of steric and electronic effects of substituents. Spectroscopies, X-ray crystallography and DFT calculations provide key guidance for our experimental synthetic work.
 

We recently proposed a fresh look at the capto-dative stabilization of radicals. This combination of electron-donating and withdrawing substituents has been known for long to stabilize C-centered radicals, but was not considered sufficient to allow for the isolation of monomeric species. On the contrary, we showed that capto-datif radicals could be isolated and air-stable representatives could even be designed! Recent advances spread from new paradigms in the mechanisms and nature of intermediates in radical reactions to novel redox active radicals (“oxyallyls”, “amino-carboxy”). These new patterns also inspired new stable carbocation and carbene scaffolds, especially for the design of ligands and their metal complexes to play further with electrons (and photons).
 

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Selected recent publications

Devillard, M., V. Regnier, J. Pécaut, and D. Martin, "Stable dicationic dioxoliums and fate of their dioxolyl radicals", Org. Chem. Front., pp. -, 2019.
Regnier, V., E. A. Romero, F. Molton, R. Jazzar, G. Bertrand, and D. Martin, "What Are the Radical Intermediates in Oxidative N-Heterocyclic Carbene Organocatalysis?.", J. Am. Chem. Soc., vol. 141, no. 2: American Chemical Society, pp. 1109–1117, 2019.
Regnier, V., Y. Planet, C. E. Moore, J. Pécaut, C. Philouze, and D. Martin, "Stable Di‐ and Tri‐coordinated Carbon(II) Supported by an Electron‐Rich β‐Diketiminate Ligand", Angew. Chemie, Int. Ed., vol. 56, no. 4: Wiley-VCH Verlag GmbH {&} Co. KGaA, pp. 1031–1035, 2017.
Regnier, V., F. Molton, C. Philouze, and D. Martin, "An air-persistent oxyallyl radical cation with simple di(methyl)amino substituents.", Chem. Commun. (Cambridge, United Kingdom), vol. 52, no. 76: Royal Society of Chemistry, pp. 11422–11425, 2016.


Collaborations

J. Pécaut (Grenoble)
G. Bertrand, R. Jazzar (USA)
C.E. Moore (USA)
 
Mis à jour le 1 juillet 2019