Metal-oxo and Metal-peroxo Complexes in Oxidative Catalysis

氧化催化中的金属-氧和金属-过氧配合物

• 批准号: 1900048
• 负责人: John Groves
• 金额: $ 84万
• 依托单位: Princeton University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-06-01 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1900048&HistoricalAwards=false
• 关键词: Metal; oxo; peroxo; Complexes; Oxidative

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.

大多数化学品都来自于几种简单的起始原料，但化学合成对美国经济产生了重大影响，占国民生产总值（GNP）的30%以上。 在这个项目中，在化学系化学催化（CAT）项目的支持下，普林斯顿大学的John格罗夫斯教授试图设计新的化学工艺来制造高价值的化学品。 这些新的合成方法可用于制备新药和农药。 这项研究结合了实验室实验和计算机计算，以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，这些金属在将碳氢（C-H）键转化为碳氟（C-F）键方面更有效。 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，特别是妇女和那些在科学领域代表性不足的人。 这些科学家获得技术培训和指导，使他们在教学，研究和工业中取得成功。超过95%的工业生产的化学品来自一小块简单的分子构建块。 化学制造业占美国国民生产总值的30%以上。 在化学系化学催化计划的资助下，普林斯顿大学的格罗夫斯教授正在开发C-H键的催化氧化、还原和拟卤化的新方法。这些方法具有根本意义，因为它们影响制药、农业化学和化学加工工业的经济价值。这种新的氧化过程的发展需要一个透彻的理解的机制，金属介导的原子转移。 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，可以以类似于氢原子转移的方式进行解剖。该项目将小分子化学催化剂与金属酶和生物催化过程的见解相结合。通过与大自然的类比，铁、锰、钴和其他金属的氧化还原化学可以显著增加对化学催化的理解和提高化学催化的能力。 普林斯顿大学的格罗夫斯小组通过NSF本科生项目研究经验，女孩科学，技术，工程和数学暑期项目（GSTEM），该奖项反映了NSF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。

项目成果

Partial Oxidation of Methane Enabled by Decatungstate Photocatalysis Coupled to Free Radical Chemistry

• DOI: 10.1021/acscatal.3c00750
• 发表时间: 2023-04
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: C. Musgrave;Kaeleigh Olsen;Nichole S. Liebov;J. Groves;W. Goddard;T. Gunnoe

Manganese Catalyzed Partial Oxidation of Light Alkanes

• DOI: 10.1021/acscatal.2c00982
• 发表时间: 2022-04
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Nathan Coutard;C. Musgrave;Jisue Moon;Nichole S. Liebov;Robert M. Nielsen;J. Goldberg;M. Li;Xiaofan Jia;Sungsik Lee;D. Dickie;W. Schinski;Zi-Shan Wu;J. Groves;W. Goddard;T. Gunnoe