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Tandem CH Activation/Arylation Catalyzed by Low‐Valent Iron Complexes with Bisiminopyridine Ligands
Author(s) -
Salanouve Elise,
Bouzemame Ghania,
Blanchard Sébastien,
Derat Etienne,
DesageEl Murr Marine,
Fensterbank Louis
Publication year - 2014
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.201304459
Subject(s) - chemistry , catalysis , radical , reactivity (psychology) , ligand (biochemistry) , tandem , redox , aryl , substrate (aquarium) , transition metal , coordination sphere , combinatorial chemistry , halide , photochemistry , reductive elimination , metal , inorganic chemistry , organic chemistry , materials science , medicine , biochemistry , alternative medicine , receptor , alkyl , oceanography , pathology , composite material , geology
Tandem CH activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox‐active non‐innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first‐row transition metals have been shown to involve substrate‐based aryl radicals, whereas our catalytic system likely involves ligand‐centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner‐sphere CH activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble‐metal‐like behavior could be sustained by the redox‐active non‐innocent bisiminopyridine ligands.