Proton and Hydride Transfer Reactions involving Organic Ions and Ion Radicals

涉及有机离子和离子自由基的质子和氢化物转移反应

• 批准号: 0074405
• 负责人: Vernon Parker
• 金额: $ 41.55万
• 依托单位: Utah State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-07-01 至 2003-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0074405&HistoricalAwards=false
• 关键词: Proton; Hydride; Transfer; Reactions; involving

With this renewal award the Organic and Macromolecular Chemistry Program supports the work of Dr. Vernon D. Parker at Utah State University in Logan, Utah. The work will extend earlier studies looking into the details of the mechanism of hydrogen transfer reactions from radical cations, positively charged organic compounds with an unpaired electron spin. Intermediates of this type are involved in a number of important biological oxidations by enzymes and industrial oxidation and polymerization reactions.The kinetics of C-H bond cleavage in various radical cations - by either proton or hydride transfer - will be studied by electrochemical and spectrophotometric methods (including stopped-flow) to determine how kinetic isotope effects depend on structure and extent of reaction. The hypothesis that many of these apparently simple bimolecular hydrogen transfer reactions actually take place by two steps with kinetically significant intermediates will be tested by experiments. The work is expected to provide valuable experience to graduate and postdoctoral students, as well as providing fundamental information of use to the organic chemical community.

有机化学和高分子化学项目支持犹他州洛根市犹他州州立大学的弗农·D·帕克博士的工作。这项工作将扩展早期的研究，探讨自由基阳离子氢转移反应的细节，自由基阳离子是带有未配对电子自旋的带正电的有机化合物。这类中间体参与了许多重要的生物氧化反应以及工业氧化和聚合反应。通过电化学和分光光度方法(包括停流)研究不同自由基阳离子中C-H键断裂的动力学，包括停流，以确定动力学同位素效应如何依赖于结构和反应程度。许多这些看似简单的双分子氢转移反应实际上是通过两个步骤与具有重要动力学意义的中间体发生的这一假设将通过实验得到检验。预计这项工作将为研究生和博士后提供宝贵的经验，并为有机化学界提供基本的使用信息。