Systematic Investigation of Relationship between Strength of NH路路路S Hydrogen Bond and Reactivity of Molybdoenzyme Models

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• 作者：Taka-aki Okamura ; Yasuhito Ushijima ; Yui Omi ; Kiyotaka Onitsuka
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：January 7, 2013
• 年：2013
• 卷：52
• 期：1
• 页码：381-394
• 全文大小：532K
• 年卷期：v.52,no.1(January 7, 2013)
• ISSN：1520-510X

文摘

A series of monooxomolybdenum(IV) and dioxomolybdenum(VI) complexes containing two intramolecular NH路路路S hydrogen bonds were synthesized and characterized by ¹H NMR, UV鈥搗isible, IR, and Raman spectroscopies, and electrochemical measurements. Elimination of the steric effects enabled the accurate and quantitative evaluation of NH路路路S hydrogen bonds. Strong correlations among the strength of the hydrogen bond, the strength of the Mo^VI鈺怬 bond, and the redox potential were clearly shown. The hydrogen bonds stabilize the intermediate in the reaction between the monooxomolybdenum(IV) and Me₃NO, resulting in acceleration of the reaction or retardation of trans鈥揷is rearrangement. The proposed intermediate and the reaction mechanism, discussed on the basis of theoretical calculations, provided a unified explanation of the reaction.