Electrochemical and Synthetic Studies of Organometallics

有机金属化合物的电化学与合成研究

• 批准号: 9400800
• 负责人: Dwight Sweigart
• 金额: $ 33万
• 依托单位: Brown University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1994
• 资助国家: 美国
• 起止时间: 1994-07-01 至 1997-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9400800&HistoricalAwards=false
• 关键词: Electrochemical; Synthetic; Studies; Organometallics

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.

通过这一奖项，无机化学、生物无机化学和金属有机化学项目支持布朗大学化学系博士德怀特·A·斯威加特对有机金属自由基的研究。对于电化学产生的17电子或19电子物种，将研究配体取代反应、反应模式的金属依赖性以及电子转移反应的速率。此外，还将研究碳氢化合物的催化配体取代和电活化。第二个研究领域是金属促进的合成吲哚、二萜和类固醇的路线。手性金属络合物将被测试为制备光学纯产品的有效试剂。在环氧杂环芳烃与金属的反应中，预计会有较高的氧化态物种形成第一个环氧杂环芳烃-金属络合物。奇电子金属有机化合物是被认为在催化反应中起重要作用的活性物种。使用电化学方法，Sweigart可以直接产生和表征这些物种，从而预测它们的反应活性。由于要研究的体系既包括均相的也包括非均相的例子，结果将提供对表面腐蚀和溶液反应的深入了解。对大的碳氢环化合物的研究具有生物学意义，建立受控的合成路线可能会对许多研究人员有用。这项研究还将扩展可用于表征化学过程的电化学方法。