Reaction Dynamics of Small Hydrocarbons

小碳氢化合物的原型异构化和裂解反应的速率和机理将被检查。选择用于研究的分子足够小，可以进行高水平的分子轨道计算，以便与实验进行比较。这些研究将包括：(1)顺、反式乙烯-1,2-d2异构化速率，(2)环丙烷-1,2-d2和环丙烷-1,2,3-d3结构异构化和几何异构化的相对能垒，(3)环丁烷-1,3-d2断裂的能垒，(4)双环1.1.0丁烷-2,2-d2转化为丁二烯的立体化学反应，(5)环戊烯中3,4-氢的消去速率和机理，(6)乙烯基环丁烷-2,3-d2与环己烯和乙烯+丁二烯反应的立体化学。这项来自有机动力学项目的资助支持了科尔盖特大学David K. Lewis教授的持续工作。这些研究结果将提供关于碳-碳和碳氢键断裂和形成过程的基本信息。关于这些过程的一个长期存在的问题是，键是逐步断开还是一步断开。这些机理方面将通过氘标记化合物和具有独特三维结构的化合物的热分解来探讨。基于复杂计算的理论预测将与实验结果进行比较，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.