期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 132, 期 23, 页码 7830-+出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja100220x
关键词
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资金
- NIH [GM-057378, GM081848]
- NSF [NSF CHE-0616190]
A new monoanionic dithiolene ligand is found in Tp*MoO(S(2)BMOQO). 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.
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