XAS CHARACT OF DIOXYGEN REACTIVE COPPER COMPLEXES IN HIGH OXIDATION STATES

铜酶与分子氧具有一系列反应性。 小分子模型提供了一种探索基本的 这个Cu/O2化学的问题，在详细和系统的方式。 几种小分子，与活性位点化学有关， O2-反应性单核、双核和三核铜酶（例如， 半乳糖氧化酶、血蓝蛋白/酪氨酸酶、漆酶、颗粒甲烷 单加氧酶）。 这些分子有着共同的 处理反应性，高度氧化的物种产生的主题， Cu/O2或Cu/氧化剂反应过程（例如，反铁磁性的 偶联的Cu（II）-酪氨酰或Cu（III）体系）。 特别是 基于小分子的Cu（III）、Cu（II）的XAS研究 配体自由基，和化学因素， 稳定这些反应性构型中的一种或另一种， 提出了

Copper enzymes exhibit a range of reactivities with dioxygen. Small molecule models offer a means of probing the fundamental problems of this Cu/O2 chemistry, in a detailed and systematic way. Several small molecules, relevant to the active site chemistries of O2-reactive mono-, bi-, and trinuclear copper enzymes, (e.g., galactose oxidase, hemocyanin/tyrosinase, laccase, particulate methane monooxygenase) have been prepared. These molecules share the common theme of addressing reactive, highly-oxidized species produced in the process of Cu/O2 or Cu/oxidant reaction (e.g., antiferromagnetically coupled Cu(II)-tyrosyl or Cu(III) systems). In particular, a small-molecule-based, XAS investigation of Cu(III), of Cu(II) coordinated to ligand radicals, and of the chemical factors which stabilize one or the other of these reactive configurations, is proposed.