Inorganic Redox Mechanisms in Aqueous Media

水介质中的无机氧化还原机制

• 批准号: 9714981
• 负责人: Edwin Gould
• 金额: $ 24.7万
• 依托单位: Kent State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-01-15 至 2001-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9714981&HistoricalAwards=false
• 关键词: Inorganic; Redox; Mechanisms; Aqueous; Media

Dr. Edwin S. Gould, Chemistry Department, Kent State University, is supported in the Inorganic, Bioinorganic, and Organometallic Chemistry Program, for investigations of aqueous phase oxidation-reduction reactions which emphasize less common oxidation states. Two areas will be studied: 1) reductions with unipositive indium and 2) metal ion catalysis of oxidations by peroxynitrite. In the first part of the study the factors that determine when In(I) reacts by 1e and when it reacts by 2e pathways will be defined. These data then will be used to determine which ligating units will allow effective inner-sphere bridging in indium (I) reactions and to learn how the reactivity of In(I) compares with that of other 2e oxo-acceptor species. In the second part of the project, the ability of transition metal catalysts to modify rates of the reactions of the peroxynitrite ion will be evaluated. In particular, conversions with both one and two electron reductants will be studied and problems associated with maintaining effective concentrations of catalytic metal centers in the high pH region necessary for the survival of peroxynitrite will be addressed. Reactions in which electrons are transferred between reactants are of enormous importance in virtually all areas of pure and applied chemistry. In this project the little studied indium +1 ion will be studied in order to develop fundamental knowledge about its ability to provide one and two electrons to chemical processes. This will provide background information to facilitate the develoment of further applications for this species. The peroxynitrite ion, the subject of the second part, is a powerful oxidant and is formed in biological systems by the coupling of nitric oxide and superoxide. Transformations of this ion with reductants are complicated by the decomposition of peroxynitrite to nitrate and this study will develop the behavior of this biologically ubiquitous and unusually reactive peroxo species. In addition to the chemical studies, an important goal of this project is the training of a cadre of chemists with a strong background in inorganic solution chemistry. This is an area of great importance, but one in which there are few young practitioners.

肯特州立大学化学系Edwin S. Gould博士在无机、生物无机和有机金属化学项目中获得支持，研究水相氧化还原反应，这些反应强调不常见的氧化态。将研究两个方面：1)用单正电铟还原和2)金属离子催化过氧亚硝酸盐氧化。在研究的第一部分中，将定义决定In(I)何时通过1e反应以及何时通过2e途径反应的因素。然后，这些数据将用于确定在铟(I)反应中哪种连接单元将允许有效的球内桥接，并了解铟(I)的反应性与其他2e氧受体的反应性如何比较。在项目的第二部分，将评估过渡金属催化剂改变过氧亚硝酸盐离子反应速率的能力。特别是，将研究与一种和两种电子还原剂的转化，并解决在高pH区维持过氧亚硝酸盐生存所需的有效催化金属中心浓度的相关问题。电子在反应物之间转移的反应在纯化学和应用化学的几乎所有领域都具有极其重要的意义。在这个项目中，我们将研究很少被研究的铟+1离子，以发展其为化学过程提供一个和两个电子的能力的基本知识。这将为进一步开发该物种的应用提供背景资料。第二部分的主题是过氧亚硝酸盐离子，它是一种强氧化剂，在生物系统中通过一氧化氮和超氧化物的偶联形成。该离子与还原剂的转化因过氧亚硝酸盐分解为硝酸盐而变得复杂，本研究将发展这种生物上普遍存在且异常活跃的过氧物种的行为。除了化学研究之外，这个项目的一个重要目标是培养一批在无机溶液化学方面有很强背景的化学家干部。这是一个非常重要的领域，但在这个领域很少有年轻的从业者。