Biradical-like Reactive Intermediates

智力上的功绩。Michl教授和他的合作者将在二十面体碳硼烷笼CB11的烷基化衍生物领域研究活性中间体、新反应和新结构，并将研究它们的更广泛的影响。他们将调查在当前授权期内发现的新反应的范围和机制，应用新技术表征其中间体，阐明观察到的取代基对碳酸性的影响，并探索一种主族金属连接到笼状碳上的新化合物。他们将致力于合成新的低聚结构，最终实现简单的三维空穴跳跃，并可能作为一种新型导电聚合物的来源。最后，他们将继续使用特别是通过部分三氟甲基化和部分氟化从CB11笼子中获得的惰性阴离子来生产和表征简单阳离子，这些阳离子可能从气相研究中已知，但超出了可分离化合物(如H3、SiH5、SiH3或Zn2)的当前溶液化学水平。更广泛的影响。该项目涉及本科生、研究生和博士后，将在一个研究小组进行，该小组传统上促进女性教育和积极的国际联系，范围高度跨学科。与物理学家的合作一直很常见，目前提议的工作涉及有机化学、无机化学、物理化学和理论化学。该组织的活动包括许多国际合作，预计每个研究生都要花几个月的时间在国外进行研究。将组织研讨会和会议，其中一些在国外。这些活动传统上涉及与工业和国家实验室的合作，并将继续这样做。结果将广泛传播。PI是一家主要评论杂志的编辑，他还经常为该杂志撰写稿件。传统的期刊发表文章和评论得到了行业期刊文章的补充。除了给专业人士讲课外，PI和小组成员还通过广播和电视向国内外的K-12学生进行公开讲座和讲座。一些国际活动发生在国际和平协会的原籍国捷克共和国，他在那里有一个兼职职位。对社会的普遍好处远远超出了对有能力的科学家的培训。过去的一些科学发现已经被工业采用(例如，锂催化烯烃聚合)，预计目前提出的一些努力也将如此(可能是用于太阳能电池或分子电子的新型导电固体，也可能是用于生产塑料电子的新材料)。

Intellectual Merit. Professor Michl and his collaborators will work on reactive intermediates, new reactions, and new structures in the area of alkylated derivatives of the icosahedral carborane cage CB11 and will examine their broader implications. They will investigate the scope and mechanism of new reactions that were discovered in the current grant period, apply new techniques for the characterization of their intermediates, elucidate the observed substituent effects on carbon acidity and explore a new group of compounds in which a main group metal is attached to the cage carbon. They will pursue the synthesis of novel oligomeric structures that ultimately promise facile three-dimensional hole hopping and could be useful as a source of a new kind of conducting polymers. Finally, they will pursue the use of especially inert anions derived from the CB11 cage by partial trifluoromethylation and partial fluorination for the production and characterization of simple cations that may be known from gas phase studies but lie beyond the current horizon of solution chemistry of isolable compounds, such as H3+, SiH5+, SiH3+, or Zn2++. Broader Impacts. The project involves undergraduate, graduate, and postdoctoral students and will take place in a research group that has traditionally promoted the education of women and active international contacts and is highly interdisciplinary in scope. Collaboration with physicists has been common and the presently proposed work involves organic, inorganic, physical, and theoretical chemistry. The group's activities include many international collaborations, and each graduate student is expected to spend a few months performing research abroad. Workshops and conferences will be organized, some abroad. The activities have traditionally involved collaborations with industry and national laboratories and will continue to do so. The results will be broadly disseminated. The PI is the editor of a major review journal, for which he also often writes contributions. Traditional journal publication of articles and reviews is complemented by articles in trade journals. In addition to lecturing to professionals, the PI and group members give public lectures and lectures to K-12 students, domestically and abroad, on the radio and TV. Some of the international activity occurs in the Czech Republic, the PI's country of origin, where he has a part-time appointment. General benefits to society go well beyond the training of competent scientists. Some of the past scientific discoveries have been taken up by industry (Li+ catalysis of alkene polymerization, for example), and it is expected that some of the efforts proposed presently will as well (possibly new kinds of electrically conducting solids for solar cell or molecular electronics, and possibly new materials for the production of plastic electronics).