Reaction Dynamics of Small Hydrocarbons

原型异构化和碎裂的速率和机理 将研究小烃的反应。选择的分子 足够小以允许高水平分子轨道 计算与实验比较。这些研究将包括：（1） 顺、反式乙烯-1，2-D2异构化速率; 结构异构化和几何异构化的能垒 环丙烷-1，2-d2和环丙烷-1，2，3-d3，（3） 环丁烷-1，3-d2的断裂，（4）立体化学 双环1.1.0丁烷-2，2-d2转化为丁二烯的转化率，（5）速率和 从环戊烯中消除分子氢的机理， 和（6）乙烯基环丁烷-2，3-D2与 环己烯和乙烯加丁二烯。 有机动力学项目的资助支持了 大卫·K.科尔盖特大学的刘易斯。这些结果 研究将提供有关过程的基本信息， 碳-碳和碳-氢键断裂并形成。一 关于这些过程的一个长期存在的问题是，债券是否 以逐步的方式或者一步一步地打破。这些机械方面 将通过标记氘的热分解来探测 化合物和具有独特三维结构的化合物。 基于复杂计算的理论预测， 与实验结果相比，这将是对理论的检验。

The rates and mechanisms of prototype isomerization and fragmentation reactions of small hydrocarbons will be examined. The molecules selected for study are sufficiently small to allow high-level molecular orbital calculation for comparison to experiment. The studies will include: (1) the rate of cis, trans ethylene-1,2-d2 isomerization, (2) the relative energy barriers for structural vs geometric isomerizations of cyclopropane-1, 2-d2 and cyclopropane-1,2,3-d3, (3) energy barriers for fragmentation of cyclobutane-1,3-d2, (4) the stereochemistry of conversion of bicyclo 1.1.0 butane-2,2-d2 to butadiene, (5) rate and mechanism of the 3,4-elimination of molecular hydrogen from cyclopentene, and (6) the stereochemistry of reactions of vinylcyclobutane-2,3-d2 to cyclohexene and to ethylene plus butadiene. This grant from the Organic Dynamics Program supports the continuing work of Professor David K. Lewis at Colgate University. These results of this research will provide fundamental information about processes where carbon-carbon and carbon-hydrogen bonds are broken and formed. A long-standing question about these processes is whether the bonds are broken in a stepwise manner or in one step. These mechanistic aspects will be probed by the thermal decomposition of deuterium labeled compounds and compounds with unique three-dimensional structure. Theoretical predictions, based on sophisticated calculations, will be compared to experimental results which will be a test of the theory.