Oxometal Complexes and Redox Catalysis

埃默里大学化学系克雷格·希尔博士的工作得到了化学系无机、生物无机和有机金属化学项目的支持。该项目涉及新的无机络合物和系统，它们使用最环保和最经济的氧化剂(氧气/空气和过氧化氢)和溶剂(水)催化转化。具体地说，这项工作由三部分组成：(A)第一部分涉及开发“无机栅栏卟啉”的等价物，以发现新的氧结合和催化氧化化学；(B)第二部分涉及具有长链有机基团的新型多铁多金属氧酸盐，其具有类似表面活性剂的性质，允许有机底物在氧化催化中更大的溶解；而(C)第三部分涉及氧在水中的催化氧化，其中热力学稳定的催化剂在周转条件下自缓冲。将制造几个新的多金属氧酸盐体系，如果被证明是坚固的，将是一类重要的低成本氧化催化剂，用于精细化学品的生产。该项目强调利用环境无害的氧化剂，如空气和含氧水来氧化有机污染物。随着对环境友好和选择性更高的催化工艺的发展，这一研究将带来巨大的社会效益。研究活动将为研究生和博士后助理提供极好的培训和教育经验。

The work of Dr. Craig Hill, Department of Chemistry, Emory University is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Division of Chemistry. The project involves new inorganic complexes and systems that catalyze transformations using the most environment friendly and economically desirable oxidants (oxygen/air and hydrogen peroxide) and solvent (water). Specifically, the work consists of a three-component program: (a) the first deals with developing "inorganic picket fence porphyrin" equivalents to uncover new oxygen binding and catalytic oxygenation chemistry; (b) the second concerns new multi-iron containing polyoxometallates with long-chain organic groups that exhibit surfactant-like properties permitting greater solubilization of organic substrates in oxidative catalysis; whereas (c) the third deals with catalytic oxidations by oxygen in water in which thermodynamically stable catalysts self-buffer under turnover conditions.Several new polyoxometallate systems will be fabricated which, if proven robust, represent an important class of low-cost oxidation catalysts for fine chemicals production. The project emphasizes utilization of environmentally benign oxidants such as air and oxygenated water to oxidize organic pollutants. The research will lead to great benefits to society as more environment friendly and selective catalytic processes are developed. The research activity will provide excellent training and educational experiences to graduate students and post-doctoral associates.