DEGRADATION OF AROMATIC AND HALOGENATED COMPOUNDS

这个项目的总体目标是设计合成金属络合物。 这将促进二氧化氧的两个氧原子并入 精选有机底物。原型金属络合物将会有 对合成有机化合物有相当大的实用价值，并将具有 对改善环境污染的潜在价值 芳香族化合物和氯代烃。其基本原理是 尝试开发这种新的氧化路线在已知的 微生物的双加氧酶酶化学 芳香族化合物氧化脱芳构化为顺式芳构化 二氢二醇形式。这种酶系统对氧化也是有效的。 优先污染物三氯乙烯的脱卤化。微生物 双加氧酶利用分子氧、NADH和一个推定的 单体铁(II)活性中心。尚未执行任何模型复合工作 在这类酶上，芳基双氧合反应是 在有机化学中史无前例。我们会努力仿效 过氧化氢及其相关O-O的制备和活化的化学 铁和锰卟啉等铁络合物上的配体 复合体。将进行系统的反应性研究，以便 提供优化反应性、效率和安全性的策略 原型金属络合物的稳定性。

The overall goal of this project is to devise synthetic metal complexes that will promote the incorporation of both oxygen atoms of dioxygen into selected organic substrates. The prototype metal complexes would have considerable utility for synthesis of organic compounds, and would be of potential value for amelioration of environmental contamination by aromatic compounds and chlorinated hydrocarbons. The rationale for attempted development of this new oxidation route is found in the known dioxygenase enzymatic chemistry of microbes that are responsible for oxidation and de-aromatization of aromatic compounds to the cis- dihydrodiol form. This enzymatic system is also effective for oxidative dehalogenation of the priority pollutant trichloroethylene. The microbial dioxygenase enzymes utilize molecular oxygen, NADH, and a putative monomeric iron(II) active site. No model compound work has been performed on this class of enzymes, and the aryl dioxygenation reaction is unprecedented in organic chemistry. Efforts will be made to emulate the chemistry by preparation and activation of peroxide and related O-O ligands on iron and manganese porphyrins and other iron chelated complexes. Systematic reactivity studies will be carried out in order to provide strategy for optimization of the reactivity, efficiency, and stability of the prototype metal complexes.