Premium
Iron and Cobalt Metallotropism in Remote‐Substituted NHC Ligands: Metalation to Abnormal NHC Complexes or NHC Ring Opening
Author(s) -
Danopoulos Andreas A.,
Massard Alexandre,
Frison Gilles,
Braunstein Pierre
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201808008
Subject(s) - chemistry , steric effects , metalation , ring (chemistry) , cobalt , tautomer , substituent , thermal decomposition , medicinal chemistry , stereochemistry , amine gas treating , metal , organic chemistry
Metallotropism of the M[N(SiMe 3 ) 2 ] 2 metal fragment in the tautomeric system IA R ⇌ AC R involving imidazolium salts/N‐heterocyclic carbenes with remote aminide/amine substituents, respectively, is manifested by its C NHC carbophilicity (R=tBu, M=Co, Fe) or NR aminido 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(SiMe 3 ) 2 } 2 ]/ IA R ⇌ AC R system are also substituent‐dependent, leading to a rearranged aminide‐functionalized aNHC Co 2 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.