Quijano Larisa Mae M, Singleton Daniel A
Department of Chemistry, Texas A&M University, College Station, 77842, United States.
J Am Chem Soc. 2011 Sep 7;133(35):13824-7. doi: 10.1021/ja2043497. Epub 2011 Aug 15.
Experimental product ratios in ozonolyses of alkyl vinyl ethers in solution do not fit with expectations based on statistical rate theories. The selectivity among cleavage pathways increases with the size of the alkyl group but to an extent that is far less than RRKM theory would predict. Trajectory studies account for the observed selectivities and support a mechanism involving a competition between cleavage of the primary ozonide and intramolecular vibrational energy redistribution. A statistical model is presented that assumes that RRKM theory holds for a molecular subset of the primary ozonides, allowing the rates of energy loss from the ozonides to be estimated from the observed product ratios.
溶液中烷基乙烯基醚臭氧分解的实验产物比例不符合基于统计速率理论的预期。裂解途径之间的选择性随着烷基大小的增加而增加，但增加的程度远低于RRKM理论的预测。轨迹研究解释了观察到的选择性，并支持了一种涉及初级臭氧化物裂解和分子内振动能量重新分布之间竞争的机制。提出了一个统计模型，该模型假设RRKM理论适用于初级臭氧化物的一个分子子集，从而可以根据观察到的产物比例估计臭氧化物的能量损失速率。
