Systematic Investigation of Relationship between Strength of NH···S Hydrogen Bond and Reactivity of Molybdoenzyme Models
| Autor: | Kiyotaka Onitsuka, Yui Omi, Yasuhito Ushijima, Taka-aki Okamura |
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| Rok vydání: | 2012 |
| Předmět: |
Models
Molecular Molybdenum Hydrogen bond Chemistry Low-barrier hydrogen bond Hydrogen Bonding Stereoisomerism Ligands Photochemistry Inorganic Chemistry symbols.namesake Intramolecular force Polymer chemistry Organometallic Compounds Proton NMR symbols Quantum Theory Reactivity (chemistry) Physical and Theoretical Chemistry Raman spectroscopy |
| Zdroj: | Inorganic Chemistry. 52:381-394 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic302149p |
| Popis: | A series of monooxomolybdenum(IV) and dioxomolybdenum(VI) complexes containing two intramolecular NH···S hydrogen bonds were synthesized and characterized by (1)H NMR, UV-visible, IR, and Raman spectroscopies, and electrochemical measurements. Elimination of the steric effects enabled the accurate and quantitative evaluation of NH···S hydrogen bonds. Strong correlations among the strength of the hydrogen bond, the strength of the Mo(VI)═O bond, and the redox potential were clearly shown. The hydrogen bonds stabilize the intermediate in the reaction between the monooxomolybdenum(IV) and Me(3)NO, resulting in acceleration of the reaction or retardation of trans-cis rearrangement. The proposed intermediate and the reaction mechanism, discussed on the basis of theoretical calculations, provided a unified explanation of the reaction. |
| Databáze: | OpenAIRE |
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