Kinetics and Mechanisms of Main-Group Redox Reactions

奥本大学的David Stanbury是由无机、生物无机和金属有机化学项目支持的，该项目研究溶液(主要是水溶液)中涉及元素周期表主族元素的氧化还原变化的反应的动力学和机理。这项研究的一个主要目的是阐明水溶液反应的机理，该反应涉及通过氧化剂的直接(外球)电子转移来氧化硫醇。第二个主要领域将涉及非质子非水溶剂中碘离子的外球氧化。第三个问题涉及羟乙胺和硫氰酸根离子的水溶液外球氧化的研究。将采用光谱(包括停流)和电化学技术。拟议的研究涉及确定在水介质中发生的相当简单的主族元素化合物的反应是快还是慢的基本过程。虽然对此类反应的研究已有一个多世纪的历史，但其反应动力学的许多基本方面直到最近才通过使用最新开发的技术和仪器而变得可用。像碘离子这样的物种的反应涉及到大量具有最高工业和生物重要性的过程，但决定这些反应动力学的微妙因素大多相当模糊。在该计划下开展的研究具有很高的内在兴趣，并将导致理解，这将适用于许多相关的研究领域。

David Stanbury of Auburn University is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry program for research on kinetics and mechanisms of reactions in solutions (mainly aqueous) that involve redox changes of elements of the main group of the periodic table. One main aim of the research is to clarify the mechanisms of aqueous solution reactions that involve oxidation of thiols by direct ('outer sphere') electron transfer from oxidants. A second main area will involve outer sphere oxidation of iodide ion in aprotic non-aqueous solvents. A third problem area involves investigations of aqueous outer-sphere oxidation of hydroxlyamine and thiocyanate ion. Spectroscopic (including stopped flow) and electrochemical techniques will be employed.The proposed research deals with the fundamental processes that determine whether the reactions of rather simple main-group element compounds that occur in aqueous media are fast or slow. Although such reactions have been studied for more than a century, many fundamental aspects of their reaction dynamics have only recently become accessible, through the use of recently developed techniques and instruments. Reactions of such species as iodide ion are involved in vast numbers of processes of the highest industrial and biological importance, but the subtle factors that determine the kinetics of these reactions are for the most part quite obscure. Research carried out under this program has high intrinsic interest, and will also lead to understanding that will be applicable in many related research areas.