Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

在这个由化学部化学催化项目资助的项目中，普林斯顿大学的约翰·格罗夫斯教授正在开发可以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反应机理和控制催化反应化学性质的因素，这将有助于优化催化结果，并增加我们的化学基础知识。碳氢化合物转化在化学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都很重要，包括那些涉及PET（正电子发射断层扫描）扫描的技术，以及药品、农用化学品和涂料的生产。所以化学为21世纪的先进技术提供了机会，并为未来培养了科学教师。格罗夫斯教授正在开发脂肪族碳氢键的催化氧化、氟化和伪卤化的新方法。这些进程仍然具有根本意义，其经济价值也大大增加。这种新型氧化过程的发展需要对金属介导的氧、卤素、活化和转移的机制有深入的了解。该项目正在进行的一个方面包括表征活性金属氧和金属过氧中间体，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)非活化C-H键氟化的新方法和机制；(2)碳-氮键形成过程中伪卤化物转移到C-H键的新催化方法；(3)在熵控制机制下利用质子调节催化C-H键氧化；(4)氧和卤素之间电催化氧转移的能量格局；(5)天然气部分氧化过程中高价碘基和碘基阳离子的C-H氧化。

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.