Biradical-like Reactive Intermediates

在化学系有机动力学项目的支持下，科罗拉多大学博尔德分校化学系的Josef Michl教授将在他的传统兴趣领域，即光物理学和光化学领域开展三个项目。其中一个项目是目前理解重原子效应的努力的延续，而两个是新的。在后者之一中，提出对负责供体-受体化合物的异常（“TICT”）发射的分子结构的古老问题采取新的攻击角度，并测试扭曲的双自由基激发态负责的提议。另一方面，提出了在复杂的构象混合物中分离和评价饱和线性链的单个构象的电子光谱性质。此外，第四个项目是在一个研究课题，这是相对较新的研究小组提出的。这是在通过最近合成CB 11（CH 3）12-、CB 11（CH 3）12. CB 11（CF 3）12-等，在PI的实验室中，以及仍然未知的CB 11（CF 3）12的拟议合成。在上一个资助期，这些化合物被证明提供了获得无机和有机金属活性中间体的新途径，它们的锂盐催化几种有机反应。现在建议探索这些新工具在有机和无机化学广泛领域的适用性。这些反应中间体的合成和性质的基础研究可能在锂电池、燃料电池膜和烯烃聚合催化剂中具有应用。

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Josef Michl, of the Department of Chemistry at the University of Colorado- Boulder, will work on three projects in the area of his traditional interest, photophysics and photochemistry. One of the projects is a continuation of a current effort to understand heavy atom effects, while two are new. In one of the latter, it is proposed to take a fresh angle of attack on the venerable problem of the molecular structure responsible for anomalous ("TICT") emission from donor-acceptor compounds, and test the proposal that a twisted biradicaloid excited state is responsible. In the other, it is proposed to separate and evaluate the electronic spectral properties of individual conformers of saturated linear chains in a complex conformer mixture. In addition, a fourth project is proposed in a research subject that is relatively new to this research group. This is a broad effort in the areas opened by the recent synthesis of carborane anions and radicals of the type CB11(CH3)12-, CB11(CH3)12., CB11(CF3)12-, etc., in the PI's laboratory, and the proposed synthesis of the still unknown CB11(CF3)12.. In the previous grant period, these compounds were shown to offer new avenues of access to inorganic and organometallic reactive intermediates, and their lithium salts catalyze several kinds of organic reactions. It is now proposed to explore the applicability of these new tools in wide areas of organic and inorganic chemistry. These fundamental studies of the synthesis and properties of reactive intermediates may have applications in lithium batteries, fuel cell membranes, and catalysts for olefin polymerization.