NITROGEN OXIDE (NOX) REDOX CHEMISTRY WITH COPPER ION

涉及氮氧化物（NOx）的化学转化 硫（SOx）具有相当大的环境和生物 重要性 工业和其他燃烧（例如，自动）过程 导致产生大量的这些化合物， 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 已知系统会影响许多涉及NOx（或SOx）的反应， 化合物，以及硫和氮的全球生物循环 涉及许多过渡金属酶催化反应。 反硝化作用是指硝酸盐的异化还原， 氮气，一种重要的厌氧细菌过程， 将大量的固定氮（肥料） 大气层 拟议研究的重点包括 铜离子催化过程的化学研究，已知 为了实现将亚硝酸根离子还原成一氧化二氮（可能 通过一氧化氮（NO）和N2 O转化为二氮。 的目标 研究计划是检查和建立基本 Cu-NOx化学方面。 调查将包括 结构和光谱表征及研究， 铜离子介导的氧化还原反应的机制，使用这些 印刷受体. 该研究计划涉及使用多齿配体， 将一种或多种铜（I）或铜（II）离子结合在已知的 和/或受控变量环境，也能够 稳定铜的氧化还原状态。 初步研究已经 表明可以制备亚硝酰基铜络合物， 结构特征和能够仿生的系统 可以建立反应性（例如，NO2-或NO与 得到N2 O）。 进一步表征和机理研究 沿着对铜离子的详细检测 与亚硝酸盐、一氧化氮和亚硝酸盐的相互作用和反应性 环氧 用于铜离子相互作用和与铜离子的反应性的新配体 亚硝酸盐、一氧化氮和一氧化二氮。 铜的新配体 并合成复合物;这些设计是为了解决 关于已经提出的反应中间体的问题，或 允许进一步研究涉及原子转移反应或 还原结合的NOx物质。 长期目标包括： NOx还原催化剂和类似化学品的开发 研究了SOx基质。

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.