Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

该奖项在无机、生物无机和有机金属化学项目中支持普林斯顿大学约翰·t·格罗夫斯教授的研究，涉及三个相互关联的领域：(1)金属卟啉介导的氧活化和转移；(2)溶液中高价铁的化学和氧化催化；(3)铑和钴卟啉的烯烃和烷烃功能化。氧-锰(V)卟啉配合物具有不寻常的反应性，具有更多的缺电子卟啉，从而形成更稳定的氧化剂。这种意想不到的行为的假设是自旋态交叉和金属配位水的酸度变化导致催化剂活性的变化。快速动力学技术将使用相关的Cr， Mn和Fe催化剂家族来验证这一假设。氧金属卟啉能以快速可逆的方式将氧配体有效地转移到溴离子上。正反应模拟卤化物过氧化物酶催化的卤化物氧化反应，逆反应为金属卟啉催化底物氧化的催化剂活化步骤。实验描述了这些反应中间体的能量学的完整映射。这些信息将用于实现次氯酸盐的催化形成和水的氧化。对烯烃的催化反马尔可夫尼科夫加氢功能化也采取了一种方法，通过分析实现催化所需的几个反应步骤和开发使这些反应可行的方法。这项研究旨在发现化学催化作用的基本原理，并利用这些见解来推动下一代催化剂的发明。这项工作还旨在培养国家实现这些发现所带来的技术进步所必需的人才，并培养未来的科学教师。氧化催化的新发现和新发明对于解决目前使用的技术所引起的制造和环境问题是必要的。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor John T. Groves at Princeton University involving research in three inter-related areas: (1) Oxygen activation and transfer mediated by metalloporphyins, (2) Chemistry and oxidative catalysis by high-valent iron in aqueous solution, (3) Alkene and Alkane functionalization by rhodium and cobalt porphyrins. Oxo-manganese(V) porphyrin complexes have an unusual reactivity profile with more electron deficient porphyrins leading to more stable oxidants. The hypothesis for this unexpected behavior is that spin state crossings and variations in the acidty of metal-coordinated water lead to variations in catalyst activity. Rapid kinetic techniques will be used to test this hypothesis using a related family of Cr, Mn, and Fe catalysts. Oxometalloporphyrins can efficiently transfer their oxo ligand to bromide ion in a rapid and reversible manner. The forward reaction mimics the halide oxidation reaction catalyzed by haloperoxidases, while the reverse reaction is the catalyst activation step in substrate oxygenation by metalloporphyrins. Experiments are described for the complete mapping of the energetics of these reactive intermediates. This information will be used to achieve the catalytic formation of hypochlorite and the oxidation of water. An approach is also being taken to the catalytic anti-Markovnikov hydrofunctionalization of olefins through the analysis of the several reaction steps required to achieve catalysis and developing methods to make these reactions practical. The research aims to discover the basic principles by which chemical catalysis operates and to use those insights to drive the invention of the next generation of catalysts. The effort also aims to train the personnel that are necessary for the nation to achieve the technological advances offered by these discoveries and to train the teachers of science for the future. New discoveries and invention in oxidative catalysis are necessary to address both manufacturing and environmental concerns arising from presently used technologies.