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Y. Liu X. M. Pan Z. S. Li X. J. Jia S. Li R. S. Wang C. C. Sun 《Theoretical chemistry accounts》2007,118(5-6):869-879
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.
Electronic Supplementary Material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
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在B3LYP/6-311+G**计算水平上, 采用导体极化连续模型研究了溶剂化效应对6-亚甲基环戊二烯酮与HCN反应生成主要产物b类酸的反应机理的影响. 计算结果表明, 在溶剂中的反应机理与在气相中的反应机理一致. 溶剂化效应使反应路径中各驻点的自由能降低, 稳定化了各物质. 溶液中的活化自由能与气相相比也有所降低, 反应更容易发生, 其中CC进攻方式的活化自由能降低得更多. 相似文献
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在MP2/6-311+G**// B3LYP/6-311+G**计算水平上, 讨论了6-亚甲基环戊二烯酮和氢氰酸(HCN)的反应机理, 得到了1个络合物, 2个中间体, 13个过渡态和8个产物. 计算结果表明, 反应存在两种进攻方式, 分别是HCN进攻CO双键和CC双键, 这两种进攻方式分别包含两种反应路径. 产物之间存在同型和异型的互变异构形式, 反应过程中得到的b类酸是最稳定的产物. 相似文献
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