Biradical-like Reactive Intermediates

在化学系有机动力学计划的支持下，科罗拉多大学博尔德分校化学系的Josef Michl教授将致力于他传统兴趣领域的三个项目，即光物理和光化学。其中一个项目是对目前理解重原子效应的努力的延续，还有两个项目是新的。在后者中，有人建议从一个新的角度来看待这个古老的问题，即分子结构对供体-受体化合物的反常(“TICT”)发射负有责任，并测试扭曲的双自由基激发态是造成这一问题的原因。另一种方法是分离和评价复杂构象混合物中饱和直链的各个构象的电子光谱性质。此外，在本课题组相对较新的研究课题中还提出了第四个项目。这是最近在PI的实验室中合成CB11(CH3)12-、CB11(CH3)12.、CB11(CF3)12-等碳硼烷阴离子和自由基所开启的广泛努力，以及建议合成仍未知的CB11(CF3)12。在之前的授权期内，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，它们的锂盐催化了几种有机反应。现在建议探索这些新工具在有机化学和无机化学的广泛领域中的适用性。这些活性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.