DEGRADATION OF AROMATIC AND HALOGENATED COMPOUNDS

本项目的总体目标是设计合成金属配合物 这将促进双氧的氧原子结合到 选择有机基质。 金属络合物的原型 对于有机化合物的合成具有相当大的实用性， 对改善环境污染的潜在价值， 芳香族化合物和氯代烃。 的理由 这种新的氧化途径的尝试性开发在已知的 微生物的双加氧酶化学， 芳族化合物氧化和脱芳构化成顺式- 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。 微生物 双加氧酶利用分子氧，NADH，和一个假定的 单体铁（II）活性位点。未进行模型化合物工作 在这类酶上，芳基二氧化反应是 在有机化学中是前所未有的。 将努力仿效 过氧化物和有关的氧-氧化合物的制备和活化化学 铁和锰卟啉和其他铁螯合物上的配体 配合物 将进行系统的反应性研究，以便 提供优化反应性、效率和 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.