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Synthesis and Reactivity of a Bio‐inspired Dithiolene Ligand and its Mo Oxo Complex
Author(s) -
Porcher JeanPhilippe,
Fogeron Thibault,
GomezMingot Maria,
Chamoreau LiseMarie,
Li Yun,
Fontecave Marc
Publication year - 2016
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.201504373
Subject(s) - reactivity (psychology) , moiety , chemistry , ligand (biochemistry) , protonation , derivative (finance) , electrochemistry , sulfur , nuclear magnetic resonance spectroscopy , mass spectrometry , cyclic voltammetry , spectroscopy , crystallography , photochemistry , stereochemistry , organic chemistry , electrode , medicine , ion , biochemistry , alternative medicine , receptor , pathology , chromatography , financial economics , economics , physics , quantum mechanics
An original synthesis of the fused pyranoquinoxaline dithiolene ligand qpdt 2− is discussed in detail. The most intriguing step is the introduction of the dithiolene moiety by Pd‐catalyzed carbon–sulfur coupling. The corresponding Mo IV O complex (Bu 4 N) 2 [MoO(qpdt) 2 ] ( 2 ) underwent reversible protonation in a strongly acidic medium and remained stable under anaerobic conditions. Besides, 2 was found to be very sensitive towards oxygen, as upon oxidation it formed a planar dithiin derivative. Moreover, the qpdt 2− ligand in the presence of [MoCl 4 ( t BuNC) 2 ] formed a tetracyclic structure. The products resulting from the unique reactivity of qpdt 2− were characterized by X‐ray diffraction, mass spectrometry, NMR spectroscopy, UV/Vis spectroscopy, and electrochemistry. Plausible mechanisms for the formation of these products are also proposed.