Kinetics and Mechanism of Main-Group Redox Reactions

奥本大学化学系的大卫斯坦伯里博士得到化学系无机、生物无机和有机物项目的支持，研究主群电子转移反应。将在水溶液中简单主族分子的一系列氧化还原反应中探讨选定化学反应的动力学和机制。 反应已经被设计成使得速率限制步骤是外层电子转移。该系统包括卤素，次氯酸盐，一氧化氮和臭氧还原，加上硫醇，硫氰酸盐和亚溴酸盐氧化，已被选定，因为它们可以广泛地促进对电子转移过程的理解。由于几个反应似乎违反了预测，即反应速率和使分子扭曲到氧化和还原结构之间的折衷几何形状所需的能量之间存在简单的相关性，因此将对马库斯理论进行测试。 电子转移反应是最基本的反应之一，在化学的许多领域都有重要的意义。这项研究将集中在涉及环境和生物系统中发生的化学过程的系统。电子如何转移到分子或从分子转移的细节将被确定。这是有意义的，因为这个项目感兴趣的几个过程似乎不遵循预测的行为或未被研究。为了了解这些化合物在环境或生物系统中的作用，必须了解它们的基本行为。

Dr. David Stanbury, Department of Chemistry, Auburn University, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for research into main-group electron-transfer reactions. The kinetics and mechanisms of selected chemical reactions will be probed in a series of redox reactions of simple main-group molecules in aqueous solution. The reactions have been designed so that the rate limiting step is outer sphere electron-transfer. The systems include halogen, hypochloride, nitric oxide, and ozone reduction, plus thiol, thiocyanate, and bromite oxidation, which have been selected because they can contribute broadly to the understanding of the electron-transfer process. As several of the reactions appear to violate the prediction that there is a simple correlation between the reaction rates and the energy required to distort the molecules to a compromise geometry between the oxidized and reduced structures, Marcus Theory will be tested. Electron-transfer is one of the most basic reactions and is of importance in many areas of chemistry. This investigation will center on systems that are involved in chemical processes occurring in the environment and in biological systems. The details of how electrons are transferred to or from a molecule will be determined. This is of significance because several of the processes of interest to this project do not appear to follow predicted behavior or are ones that are unstudied. In order to understand the role of these compounds in the environment or biological systems, their fundamental behavior must be understood.