Lewis Acids: Electron Transfer Reagents

在有机动力学项目的支持下，詹森博士将 研究金属离子催化的有机物与 水作为一种手段来确定金属的反应行为 各种络合状态的离子。金属离子对人体的 在化学过程中的作用对我们的质量至关重要， 生活，无论是从工业/经济的角度，以及 从生物学的角度来看。通过以下途径获得的信息： 探索金属离子反应性对 金属络合的状态预期可应用于 环境问题（例如，相关问题 环境中有机汞的解毒）， 新的化学变化的发展。 研究表明，汞（II）离子 促进水解的O，S-缩醛大大减少时， 该反应在阴离子存在下进行， 能够络合这种离子。该项目旨在澄清 重金属离子在这种反应中的作用，即，并 该金属简单地起刘易斯酸的作用，或者 例如，O，S-缩醛涉及硫的氧化， 电子转移到重金属离子？的影响 将所述水解促进剂从刘易斯酸改变， 电子转移试剂将通过 涉及高氧化态的动力学研究 各种过渡金属的金属络合物。快速 反应动力学（即，停流）技术将是 用于检测氧化硫物质的积聚， 假设发生在O，S-缩醛分解之前， 电子转移介导的过程。

With support from the Organic Dynamics Program, Dr. Jensen will study metal ion catalyzed reactions of organic substances with water as a means to determine the reactive behavior of metal ions in various states of complexation. Metal ions play a vital role in the chemical processes essential to our quality of life, both from an industrial/economic viewpoint as well as from a biological perspective. Information gained via exploration of the dependence of metal ion reactivity on the state of metal complexation is expected to have application to environmental problems (e.g., problems related to detoxification of organomercurials in the environment) and to the development of new chemical transformations. It has been shown that the ability of mercury(II) ions to promote hydrolysis of O,S-acetals is greatly diminished when the reaction is performed in the presence of anions that are capable of complexing this ion. The project seeks to clarify the role of the heavy metal ion in such reactions, i.e., does the metal simply function as a Lewis acid, or does the reaction with, e.g., O,S-acetals involve oxidation of sulfur via electron transfer to the heavy metal ion? The effect of changing the hydrolysis-promoting reagent from a Lewis acid reagent to an electron transfer reagent will be probed via kinetic studies that involve high oxidation state metallocomplexes of a variety of transition metals. Fast reaction kinetic (i.e., stopped-flow) techniques will be utilized to detect build-up of oxidized sulfur species that is postulated to occur prior to decomposition of the O,S-acetal in electron transfer mediated processes.