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: 1464578
• 负责人: John Groves
• 金额: $ 80万
• 依托单位: Princeton University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-06-15 至 2019-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1464578&HistoricalAwards=false
• 关键词: Metal; Oxo; Peroxo; Intermediates; Oxidative

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor John Groves of Princeton University is developing catalysts that can form carbon-fluorine bonds in hydrocarbons. Researchers on this project are also studying the reaction mechanisms and the factors that control the chemistry of the catalytic reactions, which will help to optimize the outcomes of the catalysis and to add to our fundamental knowledge base about chemistry. Hydrocarbon transformations play central roles in the chemical process industry and the global energy budget. Compounds that contain carbon-fluorine bonds are important for a range of technologies, including those involving PET (Positron Emission Tomography) scans, and the production of pharmaceuticals, agrochemicals, and coatings. So the chemistry for advanced technological opportunities in the 21st century and to train the teachers of science for the future. Professor Groves is developing new methods for the catalytic oxygenation, fluorination and pseudo-halogenation of aliphatic carbon-hydrogen bonds. Such processes continue to be of fundamental interest and of greatly increasing economic value. The development of such novel oxidative processes requires a thorough understanding of the mechanisms of metal-mediated oxygen, and halogen, activation and transfer. One ongoing aspect of the project involves characterizing reactive metal oxo and metal peroxo intermediates and elucidating the nature of their reactions with organic substrates. This research is addressing five inter-related areas: (1) New methods and mechanisms of fluorination of unactivated C-H bonds, (2) New catalytic methods for pseudo-halide transfer to C-H bonds for carbon-nitrogen bond formation, (3) Using protons to tune catalytic C-H bond oxygenation in the regime of entropy control, (4) Energy landscapes for electrocatalytic oxygen transfer to and from oxygen and halogens, (5) C-H oxygenations by high-valent iodyl and iodosyl cations for natural gas partial oxidation.

在这项由化学系化学催化计划资助的项目中，普林斯顿大学的约翰·格罗夫斯教授正在开发能够在碳氢化合物中形成碳-氟键的催化剂。该项目的研究人员还在研究催化反应的反应机理和控制化学的因素，这将有助于优化催化结果，并增加我们的化学基础知识库。碳氢化合物转化在化工过程工业和全球能源预算中发挥着核心作用。含有碳-氟键的化合物对一系列技术非常重要，包括涉及正电子发射断层扫描以及制药、农用化学品和涂料生产的技术。因此，化学为21世纪的先进技术机遇和培养面向未来的科学教师。格罗夫斯教授正在开发催化氧化、氟化和脂肪族碳氢键的假卤化的新方法。这些进程继续具有根本利益，并具有极大的经济价值。这种新型氧化过程的开发需要对金属介导的氧以及卤素的活化和转移的机制有一个透彻的了解。该项目正在进行的一个方面涉及表征活性金属氧代和金属过氧基中间体，并阐明它们与有机底物反应的性质。这项研究涉及五个相互关联的领域：(1)未活化的C-H键氟化的新方法和机理，(2)假卤化物转移到C-H键以形成碳-氮键的新催化方法，(3)在熵控制下使用质子调节催化C-H键氧化，(4)电催化氧从氧和卤素转移的能量格局，(5)高价碘和碘基阳离子对天然气部分氧化的C-H氧化。