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Article Dans Une Revue Chemistry - A European Journal Année : 2016

Synthesis and Reactivity of a Bio-inspired Dithiolene Ligand and its Mo Oxo Complex

Résumé

An original synthesis of the fused pyranoquinoxaline dithiolene ligand qpdt2− is discussed in detail. The most intriguing step is the introduction of the dithiolene moiety by Pd-catalyzed carbon–sulfur coupling. The corresponding MoIVO complex (Bu4N)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 qpdt2− ligand in the presence of [MoCl4(tBuNC)2] formed a tetracyclic structure. The products resulting from the unique reactivity of qpdt2− 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.

Domaines

Chimie
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Dates et versions

hal-01313058 , version 1 (09-05-2016)

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Jean-Philippe Porcher, Thibault Fogeron, Maria Gomez-Mingot, Lise-Marie Chamoreau, Yun Li, et al.. Synthesis and Reactivity of a Bio-inspired Dithiolene Ligand and its Mo Oxo Complex. Chemistry - A European Journal, 2016, 22 (13), pp.4447-4453. ⟨10.1002/chem.201504373⟩. ⟨hal-01313058⟩
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