The Kinetics and Mechanisms of Main-Group Redox Reactions

主族氧化还原反应的动力学和机理

• 批准号: 8913734
• 负责人: J. Howard Hargis
• 金额: $ 23.54万
• 依托单位: Auburn University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1989
• 资助国家: 美国
• 起止时间: 1989-11-15 至 1993-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8913734&HistoricalAwards=false
• 关键词: Kinetics; Mechanisms; Main; Group; Redox

The focus of this project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is the chemistry of compounds of main-group elements in aqueous solution. Main-group elements include sulfur, oxygen, chlorine, nitrogen and selenium, and the reactions of main-group compounds are involved in a variety of processes of great ecomomic and social importance, ranging from something as mundane as the action of chlorine bleach to the environmentally important formation of acid rain. The primary focus of this project is the oxidation and reduction of main-group compounds, especially through free radical intermediates. One set of reactions will use substitution-inert coordination compounds as the reaction partners, which will have the advantage of relatively predictable reaction mechanisms. Oxidation of sulfite by a Ru(III) complex will be used to estimate the standard redox potential of the sulfite radical, and is expected to demonstrate the novel process of free-radical sulfonation. This and studies with related complexes will be used to elucidate the factors affecting electron transfer at pyramidal molecules. Oxidation of NO by a Ni(III) complex will be studied to provide insight on the obscure phenomenon of nuclear tunneling. Nuclear tunneling will be probed further in studies of the outer-sphere reduction of BrCN and through kinetic isotope effects in the oxidations of nitrite ion and NO. The other class of reactions to be investigated is redox reactions between main-group molecules. The self-exchange rate for the dioxygen/superoxide couple will be measured directly. Other reactions in this class will probe the hypothesis that electron transfer between main-group species invariably proceeds with rates much greater than predicted by Marcus theory.

该项目的重点是无机，生物无机和 有机化学程序是化合物的化学 水溶液中主族元素的含量。主族元素 包括硫、氧、氯、氮和硒，且 主族化合物的反应涉及多种 具有重大经济和社会意义的进程， 从普通的氯漂白剂， 对环境有重要影响的酸雨的形成。 该项目的主要重点是氧化和 主族化合物的还原，特别是通过游离 自由基中间体一组反应将使用 取代惰性配合物作为反应 合作伙伴，这将具有相对优势， 可预测的反应机制。亚硫酸盐的氧化 Ru（III）络合物将用于估计标准氧化还原 亚硫酸根的潜力，预计将 展示了自由基磺化的新方法。这 相关复合物的研究将用于阐明 影响锥型分子电子转移的因素。 将研究通过Ni（III）络合物氧化NO以提供 对核隧穿这一模糊现象的深入了解。核 在外层的研究中将进一步探讨隧道效应 还原BrCN和通过动力学同位素效应在 亚硝酸根离子和NO的氧化。另一类反应 要研究的是主基之间的氧化还原反应 分子。分子氧/超氧化物的自交换速率 将直接测量耦合。这堂课上的其他反应 将探讨电子转移之间的假设， 主群物种总是以更大的速度前进 比马库斯理论预测的要多