Iron and Cobalt Metallotropism in Remote-Substituted NHC Ligands: Metalation to Abnormal NHC Complexes or NHC Ring Opening

Abstract : Metallotropism of the M[N(SiMe3)2]2 metal fragment in the tautomeric system IAR⇌ACR involving imidazolium salts/N‐heterocyclic carbenes with remote aminide/amine substituents, respectively, is manifested by its CNHC carbophilicity (R=tBu, M=Co, Fe) or NRaminido nitrogenophilicity (R=Cy, M=Co, Fe; R=Mes, M=Fe) and has been rationalized on the basis of steric and electronic effects. The thermolysis products of the [M{N(SiMe3)2}2]/ IAR⇌ACR system are also substituent‐dependent, leading to a rearranged aminide‐functionalized aNHC Co2 complex of an unprecedented type or to ring‐opened metallaketenimines; they are postulated to originate from different metalloisomers. The results are interpreted on the basis of the X‐ray diffraction analysis of 11 new compounds.
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Andreas Danopoulos, Alexandre Massard, Gilles Frison, Pierre Braunstein. Iron and Cobalt Metallotropism in Remote-Substituted NHC Ligands: Metalation to Abnormal NHC Complexes or NHC Ring Opening. Angewandte Chemie International Edition, Wiley-VCH Verlag, 2018, 57 (44), pp.14550-14554. ⟨10.1002/anie.201808008⟩. ⟨hal-01927645⟩

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