Theoretical studies on the reaction of pentafulvenone with water in gas phase and aqueous solvent

被引：0
作者：
Y. Liu
X. M. Pan
Z. S. Li
X. J. Jia
S. Li
R. S. Wang
C. C. Sun
机构：
[1] Northeast Normal University,Institute of Functional Material Chemistry, Faculty of Chemistry
[2] Jilin University,State Key Laboratory of Theoretical and Computational Chemistry,Institute of Theoretical Chemistry
来源：
Theoretical Chemistry Accounts | 2007年 / 118卷
关键词：
Pentafulvenone; Mechanism; Solvation effect; PCM-UAHF model; Cyclopentadienyl carboxylic acids;
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摘要：
In gas phase, the hydrations of pentafulvenone to generate three types of cyclopentadienyl carboxylic acids are studied theoretically at the MP2/6-311+G**//B3LYP/6-311+G** level. A water molecule attacking the C=O double bond of pentafulvenone can yield cyclopentadienyl carboxylic acids via the formation of fulvenediols, and attacking the C=C double bond of pentafulvenone can directly yield cyclopentadienyl carboxylic acid. The barriers of rate-determining transition states are 42.2 and 30.4 kcal  mol−1, respectively. The barriers of rate-determining transition states for two water molecules system are 20.2 and 19.6 kcal  mol−1, respectively. The products can isomerize to each other. In aqueous solvent, the hydrations of pentafulvenone are investigated using PCM-UAHF model at the MP2 (PCM)/6-311+G**// B3LYP (PCM)/6-311+G** and MP2 (PCM)/6-311+G**// B3LYP/6-311+G** levels. The barriers of all rate-determining transition states are decreased. The added water molecule acts as catalyst in both gas phase and aqueous solvent.
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页码：869 / 879
页数：10
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