Premium
Circumventing Intrinsic Metal Reactivity: Radical Generation with Redox‐Active Ligands
Author(s) -
Jacquet Jérémy,
Cheaib Khaled,
Ren Yufeng,
Vezin Hervé,
Orio Maylis,
Blanchard Sébastien,
Fensterbank Louis,
DesageEl Murr Marine
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704049
Subject(s) - redox , reactivity (psychology) , chemistry , nickel , catalysis , radical , ligand (biochemistry) , photochemistry , electrophile , electron transfer , combinatorial chemistry , inorganic chemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
Nickel complexes have gained sustained attention as efficient catalysts in cross‐coupling reactions and co‐catalysts in dual systems due to their ability to react with radical species. Central to this reactivity is nickel's propensity to shuttle through several accessible redox states from Ni 0 to Ni IV . Here, we report the catalytic generation of trifluoromethyl radicals from a nickel complex bearing redox‐active iminosemiquinone ligands. This unprecedented reactivity is enabled through ligand‐based oxidation performing electron transfer to an electrophilic CF 3 + source while the nickel oxidation state is preserved. Additionally, extension of this reactivity to a copper complex bearing a single redox equivalent is reported, thus providing a unified reactivity scheme. These results open new pathways in radical chemistry with redox‐active ligands.