Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene
Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene
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DOI：
10.1021/ja1095717
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发表时间：
2011-04-13
影响因子：
15
通讯作者：
Carpenter, Barry K.
中科院分区：
文献类型：
--
作者：
Goldman, Lawrence M.;Glowacki, David R.;Carpenter, Barry K.
分子动力学模拟揭示了双环[2.1.0]-2-烯在开环和随后的[1,5]H迁移过程中存在非统计动力学效应。这种效应的症状并不表现在反应的总体动力学或产物分支比上，这可以用主方程分析很好地解释，而是表现在两个亚甲基氢迁移的振荡偏好上。据预测，这些振荡可能对同位素标记类似物的最终产物比率产生可观察到的影响，并且在某些溶剂中的影响可能比在气相中的影响更大。
A molecular dynamics simulation reveals the occurrence of nonstatistical dynamical effects in the ring-opening and subsequent [1,5] H migration of bicyclo[2.1.0]pent-2-ene. The symptoms of the effects do not show up in the overall kinetics or product branching ratios of the reaction, which are well explained by a master-equation analysis, but in an oscillatory preference for migration of the two methylene hydrogens. It is predicted that these oscillations could have an observable effect on final product ratios in isotopically labeled analogues, and that the effect might be greater in certain solvents than in the gas phase.