title: Redox Self-Adaptation of a Nitrene Transfer Catalyst to the Substrate Needs.
abstract: The development of iron catalysts for carbon-heteroatom bond formation, which has attracted strong interest in the context of green chemistry and nitrene transfer, has emerged as the most promising way to versatile amine synthetic processes. A diiron system was previously developed that proved efficient in catalytic sulfimidations and aziridinations thanks to an FeIIIFeIVactive species. To deal with more demanding benzylic and aliphatic substrates, the catalyst was found to activate itself to a FeIIIFeIVL.active species able to catalyze aliphatic amination. Extensive DFT calculations show that this activation event drastically enhances the electron affinity of the active species to match the substrates requirements. Overall this process consists in a redox self-adaptation of the catalyst to the substrate needs.
authors.affiliation: Univ. Grenoble Alpes, CNRS UMR 5249, CEA, LCBM/pmb, 38000, Grenoble, France.
authors.forename: Eric
authors.initials: E
authors.lastname: Gouré
authors.affiliation: Univ. Grenoble Alpes, CNRS UMR 5819, CEA, SyMMES, 38000, Grenoble, France.|Center for Computational Chemistry, CRD, PRIST University Vallam, Thanjavur, Tamilnadu, India.
authors.forename: Dhurairajan
authors.initials: D
authors.lastname: Senthilnathan
authors.affiliation: Univ. Grenoble Alpes, CNRS UMR 5249, CEA, LCBM/pmb, 38000, Grenoble, France.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Coin
authors.affiliation: CCSM UMR 5246 CNRS-, Univ. Claude Bernard, Lyon 1, France.
authors.forename: Florian
authors.initials: F
authors.lastname: Albrieux
authors.affiliation: Univ. Grenoble Alpes, CNRS UMR 5249, CEA, LCBM/pmb, 38000, Grenoble, France.|LCBB, ICMMO (UMR 8182), Univ. Paris Sud, Université Paris Saclay, 91405, Orsay, France.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Avenier
authors.affiliation: Univ. Grenoble Alpes, CNRS UMR 5249, CEA, LCBM/pmb, 38000, Grenoble, France.
authors.forename: Patrick
authors.initials: P
authors.lastname: Dubourdeaux
authors.affiliation: Univ. Grenoble Alpes, CNRS UMR 5819, CEA, SyMMES, 38000, Grenoble, France.
authors.forename: Colette
authors.initials: C
authors.lastname: Lebrun
authors.affiliation: Univ. Grenoble Alpes, CNRS UMR 5819, CEA, SyMMES, 38000, Grenoble, France.
authors.forename: Pascale
authors.initials: P
authors.lastname: Maldivi
authors.affiliation: Univ. Grenoble Alpes, CNRS UMR 5249, CEA, LCBM/pmb, 38000, Grenoble, France.
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Latour
keywords: amination; homogeneous catalysis; iron; nitrene; tautomerism