Biradical-Like Reactive Intermediates

这项来自有机动力学项目的拨款支持了德克萨斯大学奥斯汀分校约瑟夫·米歇尔博士的持续工作。这项工作将为化学反应过程中形成的短寿命中间体的性质提供新的见解，并将开发使用“分子大小构建集”进行化学测量的新方法。将由米歇尔博士进行的实验分为两类。第一种是双自由基中间体，它们将通过光解或热解过程产生，然后被捕获在低温惰性气体基质中。电子和振动光谱的研究将有助于更好地了解这些不稳定物质的结构和反应性。第二类以米歇尔的烃类为中心，这是一种棒状分子，由循环的bicycloı1.1.1！戊烷 子单元。这些“分子修补玩具”为研究电子效应通过分子框架的传输提供了一个独特的机会。Michl教授还将利用这些分子的线性形状将这些分子连接在一起，形成具有明确分子结构的超分子组装体。

This grant from the Organic Dynamics Program supports the continuing work of Dr. Josef Michl at the University of Texas at Austin. This work will provide new insights into the nature of short-lived intermediates that are formed in the course of chemical reactions and will also develop new approaches to chemical measurements using a "molecular-size construction set". The experiments that will be carried out by Dr. Michl fall into two categories. The first is focused on biradical intermediates, which will be generated by photolytic or pyrolytic processes and then be trapped in a low-temperature, inert-gas matrix. Electronic and vibrational spectroscopic studies will afford an improved understanding of the structure and reactivity of these unstable species. The second category is centered on Michl's staffane hydrocarbons, which are rod-like molecules made up of recurring bicycloı1.1.1!pentane subunits. These "molecular Tinkertoys" provide a unique opportunity for studying the transmission of electronic effects through a molecular framework. Professor Michl will also take advantage of the linear shape of these molecules to link these molecules together and form supramolecular assemblies with well-defined molecular structures.