Kinetics and Mechanisms of Main-Group Redox Reactions

奥本大学的大卫斯坦伯里是由无机，生物无机和有机化学计划的研究动力学和反应机制的溶液（主要是水），涉及元素周期表的主族元素的氧化还原变化。该研究的一个主要目的是澄清水溶液反应的机制，涉及硫醇的氧化，直接（“外层”）从氧化剂的电子转移。第二个主要领域将涉及碘离子在非质子非水溶剂中的外层氧化。第三个问题领域涉及羟胺和硫氰酸根离子的水溶液外层氧化的调查。将采用光谱（包括停流）和电化学技术，研究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。尽管人们对这类反应的研究已经有世纪之久，但其反应动力学的许多基本方面直到最近才通过使用最近开发的技术和仪器而变得容易理解。碘离子等物质的反应涉及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在大多数情况下是相当模糊的。根据该计划进行的研究具有很高的内在兴趣，也将导致理解，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.