Kinetics and Mechanisms of Main-Group Reactions

该项目由无机，生物无机和 有机化学课程。 它的重点是动力学 水溶液中主族无机反应机理 溶液停流法（单波长，快速 扫描和电导检测）将用于获得动力学 数据 将使用慢速停止数据来获得速率 常数、反应速率定律和化学计量。 反应 研究内容包括：1）选择性的电子转移反应 在主组氧化还原对之间，以提供 马库斯理论适用性的严格测试， 离子半径差异很大的物种之间的反应; 2)涉及氯/二氯化物的电子转移反应， 溴/二溴化物、羟铵/羟胺和NO/NO- 作为氧化还原对，其中反应伙伴是 取代惰性配合物，导致标准 氧化还原电位和有效自交换速率常数 二酰亚胺的氢转移 (now我们有办法产生和检测这种 物种），重点是与二氧，二碘和 过氧化氢以及烯烃和单电子 氧化剂; 4）内球反应，其中亚硫酸盐是 被四氯金酸盐（III）和其他配位氧化 复合物，探索导致 连二硫酸盐中S-S键的形成; 5）NO 与氧气和三氧化硫和水反应， 与环境问题的相关性。 %%% 含有所谓主基的分子的反应 氮、硫、氯和溴等元素， 在工业和日常生活中非常重要， 例子包括饮用水的净化和 氯漂白剂在家用洗衣机中的作用。在 除了提供更好的了解有多少 这些常见的反应发生，这个项目的结果可能 提供如何避免有害副反应的见解， 如氯化过程中致癌物质的形成， 污水处理厂的废水。

This project is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program. Its focus is the kinetics and mechanisms of main-group inorganic reactions in aqueous solution. Stopped-flow methods (with single wavelength, rapid scan and conductivity detection) will be used to obtain kinetic data. The stopped-slow data will be used to obtain rate constants, reaction rate laws and stoichiometries. Reactions to be studied include: 1) Selected electron transfer reactions between pairs of main-group redox couples, in order to provide stringent tests of the applicability of Marcus theory to reactions between species of widely differing ionic radii; 2) electron transfer reactions involving chlorine/dichloride, bromine/dibromide, hydroxylammonium/hydroxylamine, and NO/NO- as redox couples, where the reaction partners are substitution-inert coordination complexes, leading to standard redox potentials and effective self-exchange rate constants for the main-group couples; 3) dihydrogen transfer from diimide (now that methods are available to generate and detect this species) with emphasis on reactions with dioxygen, diiodine and hydrogen peroxide, as well as with olefins and one-electron oxidants; 4) inner-sphere reactions in which sulfite is oxidized by tetrachloroaurate(III) and other coordination complexes, probing the mechanistic factors that lead to formation of the S-S bond in dithionate; 5) the reactions of NO with dioxygen and of sulfur trioxide with water, because of their relevance to environmental issues. %%% Reactions of molecules containing the so-called main-group elements, such as nitrogen, sulfur, chlorine and bromine, are of great importance in industry and in everyday life, with examples including the purification of drinking water and the action of chlorine bleach in the home washing machine. In addition to providing a better understanding of how many of these common reactions occur, the results of this project may provide insight into how to avoid detrimental side reactions, such as the formation on carcinogens during the chlorination of sewage plant effluents.