Noninnocent Dithiolene Ligands: A New Oxomolybdenum Complex Possessing a Donor−Acceptor Dithiolene Ligand

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• 作者：Kelly G. Matz ; Regina P. Mtei ; Belinda Leung ; Sharon J. Nieter Burgmayer ; Martin L. Kirk
• 刊名：Journal of the American Chemical Society
• 出版年：2010
• 出版时间：June 16, 2010
• 年：2010
• 卷：132
• 期：23
• 页码：7830-7831
• 全文大小：145K
• 年卷期：v.132,no.23(June 16, 2010)
• ISSN：1520-5126

文摘

A new monoanionic dithiolene ligand is found in Tp*MoO(S₂BMOQO). A combination of X-ray crystallography, electronic absorption spectroscopy, resonance Raman spectroscopy, and bonding calculations reveal that the monoanionic dithiolene ligand possesses considerable thiolate-thione character resulting from an admixture of an intraligand charge transfer excited state into the ground state wave function. The unusual dithiolene exhibits a highly versatile donor−acceptor character that dramatically affects the Mo(IV/V) redox couple and points to a potentially noninnocent role of the pterin fragment in pyranopterin Mo enzymes.