Monooxomolybdenum(VI) Complexes Possessing Olefinic Dithiolene Ligands: Probing Mo−S Covalency Contributions to Electron Transfer in Dimethyl Sulfoxide Reductase Family Molybdoenzymes
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- 作者：Hideki Sugimoto ; Susumu Tatemoto ; Koichiro Suyama ; Hiroyuki Miyake ; Regina P. Mtei ; Shinobu Itoh ; Martin L. Kirk
- 刊名：Inorganic Chemistry
- 出版年：2010
- 出版时间：June 21, 2010
- 年：2010
- 卷：49
- 期：12
- 页码：5368-5370
- 全文大小：721K
- 年卷期：v.49,no.12(June 21, 2010)
- ISSN：1520-510X
文摘
A monooxomolybdenum(VI) model complex for the oxidized active site in the DMSOR family of molybdoenzymes has been synthesized and structurally characterized. The compound was obtained from the desoxomolybdenum(IV) derivative by clean oxygen-atom transfer from an amine N-oxide in a manner similar to that observed in the enzyme. A combination of electronic absorption and resonance Raman spectroscopies, coupled with the results of bonding and excited-state calculations, has been used to provide strong support for a highly covalent Mo(dxy)−S(dithiolene) π*-bonding interaction in the molybdenum(VI) complex. It is proposed that the resulting Mo−S covalency facilitates electron-transfer regeneration of the catalytically competent DMSOR MoIV active site.