Inorganic Redox Mechanisms in Aqueous Media

肯特州立大学化学系的埃德温·S·古尔德博士在无机化学、生物无机化学和金属有机化学计划中得到支持，主要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)单正离子铟的还原；2)金属离子催化过亚硝酸根的氧化。在研究的第一部分，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。这些数据将被用来确定哪些连接单元将允许铟(I)反应中有效的球内桥联，并了解In(I)的反应活性与其他2E氧受体物种的反应活性如何比较。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根离子反应速率的能力。特别是，将研究单电子和双电子还原剂的转化，并解决与在高pH区保持催化金属中心有效浓度相关的问题，这是过氧亚硝酸盐生存所必需的。在纯化学和应用化学的几乎所有领域中，电子在反应物之间转移的反应都是非常重要的。在这个项目中，我们将研究很少被研究的铟+1离子，以发展关于它为化学过程提供一个和两个电子的能力的基础知识。这将为进一步开发该物种的应用提供背景信息。过亚硝酸根离子是第二部分的主题，是一种强大的氧化剂，在生物系统中由一氧化氮和超氧化物偶联而形成。由于过氧亚硝酸盐分解为硝酸盐，这种离子与还原剂的转化变得复杂，这项研究将发展这种生物上普遍存在的、异常活跃的过氧物物种的行为。除了化学研究，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具有深厚背景的化学家干部。这是一个非常重要的领域，但年轻实践者很少。

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.