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

提出的工作建立在先前的结果在两个主要领域的配位化学与苯氧基。拟建项目的第一个领域涉及基于易氧化含酚配体与过渡金属离子的使用的制备配位化学。所得到的配合物将通过不同的光谱方法（UV-VIS，共振拉曼，EPR和最终Mössbauer），磁化率测量和x射线晶体学进行表征。重点将放在一般的电化学氧化还原过程上，特别是在电化学生成的含苯氧基物质上。在提出的工作的第二个领域，我们将开发高效的仿生催化剂基于苯氧基的容易形成的酒精和胺的空气氧化。这些模型催化剂应该能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的含铜和含铁系统。初步结果表明，使用最近合成的配位化合物将揭示关于“酶催化中的自由基”的丰富新知识，包括含铜酶半乳糖氧化酶和胺氧化酶的功能模型。我们将在这一初步工作的基础上，大大增加金属-苯氧基的化学范围。本项目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.