Synthesis and Reactivity of a Bio‐inspired Dithiolene Ligand and its Mo Oxo Complex |
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| Authors: | Jean‐Philippe Porcher Thibault Fogeron Dr Maria Gomez‐Mingot Lise‐Marie Chamoreau Dr Yun Li Prof Marc Fontecave |
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| Institution: | 1. Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Université Paris 6, Paris CEDEX 05, France;2. Sorbonne Universités, UPMC Université Paris 6, Institut Parisien de Chimie Moléculaire, UMR 8232 CNRS, Paris CEDEX 05, France |
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| Abstract: | 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)2MoO(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. |
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| Keywords: | cross-coupling molybdenum protonation dithiolene ligands sulfur heterocycles |
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