Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

氧化催化中的金属-氧和金属-过氧中间体

• 批准号: 0616633
• 负责人: John Groves
• 金额: $ 78.8万
• 依托单位: Princeton University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-08-01 至 2012-02-29
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0616633&HistoricalAwards=false
• 关键词: Metal; Oxo; Peroxo; Intermediates; Oxidative

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.

这个奖项在无机，生物无机和有机化学计划支持研究教授约翰T。格罗夫斯在普林斯顿大学，涉及三个相互关联的领域的研究：（1）由金属卟啉介导的氧活化和转移，（2）在水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官能化。 氧代-锰（V）卟啉络合物具有不寻常的反应性特征，更多的缺电子卟啉导致更稳定的氧化剂。 这种意外行为的假设是，自旋状态交叉和金属配位水的酸性变化导致催化剂活性的变化。快速动力学技术将被用来测试这一假设，使用相关的家庭的铬，锰，铁催化剂。 氧代卟啉能快速、可逆地将其配体与溴离子进行有效的配位。正向反应模拟卤过氧化物酶催化的卤化物氧化反应，而反向反应是金属卟啉氧化底物中的催化剂活化步骤。 实验描述了这些活性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。 通过分析实现催化所需的几个反应步骤并开发使这些反应实用的方法，还正在采取一种方法来对烯烃进行催化反马尔科夫氢官能化。该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。这项努力的目的还在于培训国家实现这些发现所提供的技术进步所必需的人员，并为未来培训科学教师。 氧化催化的新发现和发明对于解决目前使用的技术引起的制造和环境问题是必要的。