Homogeneous catalysis of aerobic oxidation of alcohols and amines: Biomimetic metal-phenoxyl radical reactivity

拟议的工作建立在先前的结果在两个主要领域的配位化学与菲自由基。第一个领域的拟议项目涉及与制备配位化学的基础上使用容易氧化的含酚配体与过渡金属离子。将通过不同的光谱方法（紫外-可见光、共振拉曼、EPR和最终的穆斯堡尔谱）、磁化率测量和X射线晶体学来表征所产生的复合物。重点将放在一般的电化学氧化还原过程，特别是电化学产生的含酚类物质。在第二个领域的工作中，我们将开发有效的仿生催化剂的基础上容易形成的苯氧基自由基的空气氧化的醇和胺。这些模型催化剂应该在比酶更广泛的底物和更苛刻的条件下工作。重点将集中在作为工业催化剂的重要性的含铜和含铁系统。初步结果表明，最近合成的配位化合物的使用将揭示丰富的新知识，关于“自由基的酶催化”，其中包括功能模型不仅含铜的酶半乳糖氧化酶，但也胺氧化酶。我们将建立在这一初步工作，大大增加了金属苯氧基自由基的化学范围。建议的项目预计将对化学和催化科学产生广泛的影响，并为学生提供现代无机化学的良好学习机会。

The proposed work builds on prior results in two major areas of coordination chemistry with phenoxyl-radicals. The first area of proposed project is involved with the preparative coordination chemistry based on the use of easily oxidizable phenolcontaining ligands with transition metal ions. The resulting complexes will be characterized by different spectroscopic methods (UV-VIS, resonance Raman, EPR and eventually Mössbauer), magnetic susceptibility measurements and by X-ray crystallography. Emphasis will be given on the electrochemical redox processes in general and in particular on the electrochemically generated phenoxyl-containing species. In the second area of proposed work we will develop efficient biomimetic catalysts based on the facile formation of phenoxyl radical for aerial oxidation of alcohols and amines. These model catalysts should work on a wider range of substrates and in harsher conditions than enzymes can. Emphasis will be focussed on copper- and iron-containing systems of importance as industrial catalysts. Preliminary results indicate that the use of recently synthesized coordination compounds will uncover a wealth of new knowledge regarding "radicals in the enzymatic catalysis" that includes functional models not only of the copper-containing enzyme galactose oxidase but also of amine oxidases. We will build on this preliminary work to greatly increase the scope of the chemistry of metal-phenoxyl radical. The proposed project is expected to have wide impact on chemical and catalytic science as well as providing excellent learning opportunities in modern inorganic chemistry for students.