Hydration effects on the reaction with an open-shell transition state: QM/MM-ER study for the dehydration reaction of alcohol in hot water

Hideaki Takahashi, Fumihiro Miki, Hajime Ohno, Ryohei Kishi, Suguru Ohta, Shin ichi Furukawa, Masayoshi Nakano

研究成果: ジャーナルへの寄稿学術論文査読

9 被引用数 (Scopus)

抄録

The reaction mechanism for the dehydration of 1,4-butanediol in hot water has been investigated by means of the hybrid quantum mechanical/molecular mechanical approach combined with the theory of energy representation (QM/MM-ER). We have assumed that the proton transfers along the hydrogen bonds of the water molecules catalyze the reaction, where the transition state (TS) forms a singlet biradical electronic structure. It has been revealed by the simulation that the biradical electronic state at the TS changes to zwitterionic structure in solution due to the hydration of the polar solvent. Such the electronic structure change gives rise to the substantial stabilization of the TS in hot water. As a result, the water-catalytic path becomes more favorable in aqueous solution than another possible path that proceeds without proton transfers as opposed to the reaction mechanism in the gas phase. Furthermore, the activation free energy computed by the present method is in excellent agreement with the experimental result.

本文言語英語
ページ(範囲)781-794
ページ数14
ジャーナルJournal of Mathematical Chemistry
46
3
DOI
出版ステータス出版済み - 2009 8月

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