Electrochemical and Synthetic Studies of Organometallics

通过这个奖项，无机、生物无机和有机金属化学项目支持布朗大学化学系Dwight A. Sweigart博士对有机金属自由基的研究。配体取代反应，金属对反应模式的依赖，以及电子转移反应的速率将研究电化学生成的17或19电子种。此外，还将研究催化配体取代和碳氢化合物的电活化。第二个研究领域是金属促进合成吲哚、二萜和类固醇的途径。手性金属配合物将作为制备光学纯产品的有效试剂进行测试。高氧化态的物质在氧烯与金属的反应中形成第一个氧烯-金属配合物。奇电子有机金属化合物是一种在催化反应中起重要作用的活性物质。使用电化学方法，Sweigart可以直接生产和表征这些物质，从而预测它们的反应性。因为要研究的系统包括均相和非均相的例子，结果将提供深入了解表面腐蚀以及溶液反应。大碳氢环化合物的研究具有生物学相关性，建立受控的合成路线可能对许多研究人员有用。该研究还将扩展用于表征化学过程的电化学方法。

With this award, the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on organometallic radicals by Dr. Dwight A. Sweigart of the Chemistry Department, Brown University. Ligand substitution reactions, metal dependence of reactivity patterns, and rates of electron transfer reactions will be investigated for electrochemically generated 17- or 19- electron species. In addition, catalytic ligand substitution and electroactivation of hydrocarbons will be studied. A second area of investigation is metal-promoted synthetic routes to indoles, diterpenes, and steroids. Chiral metal complexes will be tested as effective reagents in the preparation of optically pure products. High oxidation state species are expected in the reaction of oxirenes with metals to form the first oxirene-metal complexes. Odd-electron organometallic compounds are reactive species thought to play important roles in catalytic reactions. Using electrochemical methods, Sweigart can produce and characterize these species directly and thus predict their reactivities. Because the systems to be studied include both homogeneous and heterogenous examples, the results will provide insight into surface corrosion as well as solution reactions. The investigation of large hydrocarbon ring compounds is biologically relevant and establishing controlled synthetic routes may prove useful to many investigators. The study will also extend the electrochemical methods available for characterizing chemical processes.