Reactions Involving Main-Group Radicals in Solution

溶液中涉及主族自由基的反应

• 批准号: 0509889
• 负责人: David Stanbury
• 金额: $ 40.5万
• 依托单位: Auburn University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-09-01 至 2010-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0509889&HistoricalAwards=false
• 关键词: Reactions; Involving; Main; Group; Radicals

Dr. David Stanbury, Department of Chemistry, Auburn University, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Division for research into kinetics and mechanisms of reactions of main group radicals. A series of four research projects will be undertaken. The first will be on the reactions of iodide with one-electron outer-sphere transition-metal oxidants in nonaqueous solutions. Interest in these reactions arises from their relevance to photoelectrochemical cells, where oxidation of iodide in nonaqueous media by related oxidants is an essential component of their design. The second focuses on reactions of the thiols cysteine and glutathione in aqueous media with classical outer-sphere transition-metal oxidants. In this case the motivation is the relevance of the work to biochemistry, since these two thiols are the primary redox-active sulfur compounds in living organisms. The third is an investigation of the oxidation of hydroxylamine by classic outer-sphere oxidants in aqueous media. This reaction poses a conundrum, because simple electron-transfer oxidation is ruled out by thermochemical considerations; a hydrogen-atom-transfer mechanism is suggested, which is quite unusual among reactions of main-group species in aqueous solution. The fourth is a study of the aqueous oxidation of nitric oxide with chlorite. Here, electron transfer seems to be quite unlikely, and a variety of atom-transfer mechanisms are suggested; the reaction has not been studied before, but it is crucial to the operation of flue gas scrubbers in the petrochemical industry.In this project new classes of reactivity will be uncovered. As mentioned above, the iodide project will contribute to developing solar energy technology. The thiol project will contribute to the understanding of general sulfur metabolism. The hydroxylamine project will contribute to an understanding of biological nitrification. The nitric oxide/chlorate project will aid in the development of improved technologies for abatement of pollution by nitrogen oxides. The projects will strengthen the scientific infrastructure of society through the advanced training and education of undergraduate, graduate, and postdoctoral students.

David Stanbury博士，奥本大学化学系，受化学系无机、生物无机和有机金属化学项目支持，研究主要基团自由基反应的动力学和机理。将进行一系列的四个研究项目。第一章是关于碘化物与单电子外球过渡金属氧化剂在非水溶液中的反应。对这些反应的兴趣源于它们与光电化学电池的相关性，在光电化学电池中，由相关氧化剂氧化非水介质中的碘化物是其设计的重要组成部分。第二部分着重于半胱氨酸和谷胱甘肽在水介质中与经典外球过渡金属氧化剂的反应。在这种情况下，动机是与生物化学相关的工作，因为这两种硫醇是生物体内主要的氧化还原活性硫化合物。第三是研究了经典的外球氧化剂在水介质中氧化羟胺。这个反应是一个难题，因为简单的电子转移氧化被热化学的考虑排除了；提出了一种氢原子转移机理，这在水溶液中主要基团的反应中是很少见的。四是研究了亚氯酸盐对一氧化氮的水氧化作用。在这里，电子转移似乎不太可能，并提出了各种各样的原子转移机制；该反应在石油化工烟气洗涤器的运行中起着至关重要的作用。在这个项目中，新的反应性类别将被发现。如上所述，碘化物项目将有助于发展太阳能技术。硫醇项目将有助于理解一般的硫代谢。羟胺项目将有助于对生物硝化的理解。一氧化氮/氯酸盐项目将有助于发展改进的技术，以减少氮氧化物的污染。这些项目将通过对本科生、研究生和博士后的高级培训和教育，加强社会的科学基础设施。