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



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



Chemistry 22(13): 4447-4453



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 (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 qpdt(2-) ligand in the presence of [MoCl4 (tBuNC)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.

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Accession: 058953309

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PMID: 26880579

DOI: 10.1002/chem.201504373


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