NITROGEN OXIDE (NOX) REDOX CHEMISTRY WITH COPPER ION

涉及氮氧化物(NOx)的化学转化 和硫磺(SOX)具有相当大的环境和生物意义 重要性。工业和其他燃烧(例如，汽车)过程 导致大量这些化合物的产生， 它们通过造成空气污染来威胁我们的环境， 酸雨和不可接受的“温室气体”效应。生物学 众所周知，系统会影响许多涉及氮氧化物(或SOx)的反应。 化合物与硫和氮的全球生物循环 涉及许多过渡金属酶催化的反应。 反硝化是硝酸盐异化还原为 氮气，一种重要的厌氧细菌过程 将相当数量的固定氮(肥料)归还给 大气层。拟议研究的重点包括 已知的铜离子催化过程的化学研究 将亚硝酸根离子还原为一氧化二氮(可能 通过一氧化氮(NO)和N2O转化为氮素。的目标是 研究计划是检查和建立基本的 铜-氮氧化物化学的几个方面。调查将包括 结构和光谱表征及相关研究 铜离子介导的氧化还原反应的机理 底物。 研究计划涉及使用多齿配体，能够 结合一个或多个铜(I)或铜(II)离子 和/或受控的可变环境，还能够 稳定两种铜的氧化还原状态。初步研究表明 结果表明，亚硝基铜络合物可以制备， 结构特征和能够仿生的系统 可以建立反应性(例如，NO2-或NO对 释放N2O)。进一步的表征和机理研究 以及对铜离子的详细研究 与亚硝酸盐、一氧化氮和亚硝酸盐的相互作用和反应性 氧化物。铜离子相互作用及其活性的新配体 亚硝酸盐、一氧化氮和一氧化二氮。铜的新型配体 和复合体将被合成；这些旨在解决 关于已提出的反应中间体或 允许进一步研究涉及原子转移反应或 结合态NOx物种的减少。较长远的目标包括 NOx还原催化剂及其类似物的研究进展 关于SOX底物的研究。

Chemical transformations involving the oxides of nitrogen (NOx) and sulfur (SOx) are of considerable environmental and biological importance. Industrial and other combustion (e.g., auto) processes result in the production of large quantities of these compounds, which threaten our environment by contributing to air pollution, acid rain and unacceptable "greenhouse" gas effects. Biological systems are known to effect many reactions involving NOx (or SOx) compounds, and global biological cycles of sulfur and nitrogen involve many transition-metal enzyme catalyzed reactions. Denitrification is the dissimilatory reduction of nitrate to nitrogen gas, an important anaerobic bacterial process which returns considerable quantities of fixed nitrogen (fertilizer) to the atmosphere. The focus of the proposed research involves studies of the chemistry of copper ion catalyzed processes, known to effect the reduction of nitrite ion to nitrous oxide (possibly through nitric oxide, NO) and N2O to dinitrogen. The objective of the research program is to examine and establish fundamental aspects of Cu-NOx chemistry. The investigations will include structural and spectroscopic characterization and studies involving the mechanisms of copper ion mediated redox reactions using these substrates. The research plan involves the use of polydentate ligands capable of binding one or more copper(I) or copper(II) ions in a known and/or controlled variable environment, one that is also capable of stabilizing both copper redox states. Preliminary studies have shown that copper nitrosyl complexes can be prepared and structurally characterized and that systems capable of biomimetic reactivity can be established (e.g. the reaction of NO2- or NO to give N2O). Further characterization and mechanistic investigations are proposed, along with detailed examination of copper ion interactions and reactivity with nitrite, nitric oxide and nitrous oxide. New ligands for copper ion interactions and reactivity with nitrite, nitric oxide and nitrous oxide. New ligands for copper and complexes will be synthesized; these are designed to address questions concerning already proposed reaction intermediates or allow for further studies involving atom transfer reactions or reduction of bound NOx species. Longer term objectives include the development of catalysts for NOx reduction and analogous chemical studies with SOx substrates.