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Powerful Fluoroalkoxy Molybdenum(V) Reagent for Selective Oxidative Arene Coupling Reaction
Author(s) -
Schubert Moritz,
Leppin Jana,
Wehming Kathrin,
Schollmeyer Dieter,
Heinze Katja,
Waldvogel Siegfried R.
Publication year - 2014
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.201309287
Subject(s) - reagent , chemistry , molybdenum , reactivity (psychology) , oxidative coupling of methane , cationic polymerization , combinatorial chemistry , selectivity , coupling reaction , photochemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
We introduce the novel fluoroalkoxy molybdenum(V) reagent 1 which has superior reactivity and selectivity in comparison to MoCl 5 or the MoCl 5 /TiCl 4 reagent mixture in the oxidative coupling reactions of aryls. Common side reactions, such as chlorination and/or oligomer formation, are drastically diminished creating a powerful and useful reagent for oxidative coupling. Theoretical treatment of the reagent interaction with 1,2‐dimethoxybenzene‐type substrates indicates an inner‐sphere electron transfer followed by a radical cationic reaction pathway for the oxidative‐coupling process. EPR spectroscopic and electrochemical studies, X‐ray analyses, computational investigations, and the experimental scope provide a highly consistent picture. The substitution of chlorido ligands by hexafluoroisopropoxido moieties seems to boost both the reactivity and selectivity of the metal center which might be applied to other reagents as well.