Dynamics of the degenerate rearrangement of bicyclo[3.1.0]hex-2-ene
Dynamics of the degenerate rearrangement of bicyclo[3.1.0]hex-2-ene
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DOI：
10.1021/ja050722w
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发表时间：
2006-01-11
影响因子：
15
通讯作者：
Houk, KN
中科院分区：
文献类型：
--
作者：
Doubleday, C;Suhrada, CP;Houk, KN
拟经典直接动力学模拟应用于产生非统计积分布的4重简并重排。模拟产物比与实验结果吻合，完全是动态决定的。轨迹寿命在一个低频振动周期的数量级上。反应动量与势面几何特征的相互作用产生选择性，尽管存在共同的能垒。描述了一种几何模型，用于定性地估计许多动态确定的产物比，而不依赖于轨迹计算。该反应的特点预计也适用于其他涉及适度稳定的二自由基中间体的反应。
Quasiclassical direct dynamics simulations are applied to a 4-fold degenerate rearrangement which yields a nonstatistical product distribution. The simulated product ratio agrees with experiment and is found to be entirely dynamically determined. Trajectory lifetimes are on the order of a low-frequency vibrational period. The interaction of reaction momentum with the geometric features of the potential surface produces selectivity despite a common energy barrier. A geometric model is described for qualitatively estimating much of the dynamically determined product ratio independently of trajectory calculations. The characteristics of this reaction are expected also to apply to others involving modestly stabilized diradical intermediates.