Metal-oxo and Metal-peroxo Complexes in Oxidative Catalysis

大多数化学品都来自几种简单的起始材料，但化学合成对美国经济产生了重大影响，贡献了国民生产总值（GNP）的30%以上。在这个项目中，普林斯顿大学的约翰·格罗夫斯教授在化学系化学催化（CAT）项目的支持下，寻求设计新的化学工艺来制造高价值的化学品。新的合成方法可用于制造新的药物和农药。这项研究结合了实验室实验和计算机计算来预测和验证反应的进展。这项工作的最终目标是用更便宜的金属取代昂贵的金属催化剂，这种金属更有效地将碳氢（C-H）键转化为碳-氟（C-F）键。这项研究阐明了新化学反应的详细途径。格罗夫斯教授的研究小组培养未来的科学家，特别是女性和那些在科学领域代表性不足的人。这些科学家获得了技术培训和指导，因此他们在教学、研究和工业领域取得了成功。超过95%的工业生产的化学物质来源于一小块简单的分子构建块。化工制造业对美国国民生产总值的贡献超过30%。在化学学部化学催化项目的资助下，普林斯顿大学的格罗夫斯教授正在开发碳氢键的催化氧化、氟化和伪卤化的新方法。这些过程具有根本的利益，因为它们影响到制药、农用化学和化学加工工业的经济价值。这种新型氧化过程的发展需要对金属介导的原子转移机制有透彻的了解。该项目旨在通过表征活性金属氧和金属过氧中间体并阐明其与有机底物反应的性质来观察催化的单一过程。特别是，该研究阐述了杂原子反弹催化（HRC）的概念基础，可以用类似于氢原子转移的方式进行剖析。该项目将小分子化学催化剂与金属酶和生物催化过程相结合。通过与自然的类比，铁、锰、钴和其他金属的氧化还原化学可以大大增加对化学催化的理解和提高能力。普林斯顿大学的格罗夫斯小组通过NSF本科生项目的研究经验、女孩科学、技术、工程和数学暑期项目（GSTEM）和普林斯顿化学暑期多样性项目，培养学生和博士后研究助理，尤其是代表性不足的少数民族和女性。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

Most chemicals derive from a just a few simple starting materials yet chemical synthesis has a major impact on the economy of the United States, contributing more than 30% of the Gross National Product (GNP). In this project, with the support from the Chemical Catalysis (CAT) Program in the Division of Chemistry, Professor John Groves of Princeton University seeks to design new chemical processes to make high value chemicals. The new synthetic methods may be used to make new drugs and agrichemicals. The research combines laboratory experiments and computer calculations to predict and verify how the reactions progress. The ultimate goal of this work is to replace expensive metal catalysts with less inexpensive metals that are more effective in convert carbon-hydrogen (C-H) bonds to carbon-fluorine (C-F) bonds. This research illustrates the detailed pathways for the new chemical reactions. The research group of Professor Groves trains future scientists, especially women and those that are under-represented in science. These scientists gain both technical training and mentoring so that they are successful in careers in teaching, research, and industry.More than 95% of industrially-produced chemicals are derived from a small slate of simple, molecular building blocks. Chemical manufacturing contributes more than 30% of the GNP of the United States. With funding from the Chemical Catalysis Program of the Chemistry Division, Professor Groves of Princeton University is developing new methods for the catalytic oxygenation, fluorination and pseudo-halogenation of C-H bonds. Such processes are of fundamental interest as they inpact the economic value of the pharmaceutical, agrochemical and chemical process industries. The development of such novel oxidative processes requires a thorough understanding of the mechanisms of metal-mediated atom transfer. The project aims to observe the unitary processes of catalysis by characterizing reactive metal oxo and metal peroxo intermediates and elucidating the nature of their reactions with organic substrates. In particular, the research elaborates a conceptual basis for heteroatom rebound catalysis (HRC), which can be dissected in a manner similar to hydrogen atom transfer. The project integrates small molecule chemical catalysts with insights from metalloenzymes and biocatalytic processes. Through analogies with Nature, the redox chemistry of iron, manganese, cobalt and other metals can add significantly to understanding and increased capabilities in chemical catalysis. The Groves group at Princeton University trains students and postdoctoral research associates, especially under-represented minorities and women, through the NSF Research Experiences for Undergraduates Programs, the Girls Science, Technology, Engineering and Mathematics Summer Program (GSTEM), and Princeton Chemistry's summer diversity program.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.