CAS: Metal-oxo and Metal-peroxo Complexes in Oxidative Catalysis

在化学系化学催化计划的资助下，普林斯顿大学的约翰·T·格罗夫斯教授和他的研究小组将开发和研究催化剂，使C-H活化等节能的化学转化更好地获得高附加值的化学产品。超过95%的化学工业产品来自于一小部分与美国30%以上的GNP相关的分子构件。该项目的中心论点是，氧化化学和生物化学催化的最新概念进展，以及新兴实验技术和现代理论的相互作用，为开发廉价、富含地球的过渡金属作为这些选择性过程的催化剂提供了前所未有的机会。该项目将微生物使用的生物催化知识与来自合成系统的见解结合在一起，为理解这些过程提供了概念基础。该化学的广泛应用将对国家和世界的化学和能源经济产生重大影响。格罗夫斯小组将继续作为研究生和博士后研究助理的有效培训基地，特别是妇女和科学界代表性不足群体的成员。在这个项目中，Groves教授的目标是开发C-H键的催化氧化、氟化和卤化的新方法。发展新的有效的氧化过程需要通过观察单一的催化过程，包括一系列金属-卤素物种，并阐明它们与有机底物反应的性质，来彻底了解金属介导的原子转移的机理。特别是，拟议的研究努力阐述杂原子反弹催化的概念基础，这种催化可以用类似于氢原子转移的方式进行剖析。该项目将把小分子化学催化剂与来自金属酶和生物催化过程的见解结合起来。自然界使用铁蛋白来实现C-H羟化和卤化反应。通过类比，Fe、Mn、Co和其他丰富的过渡金属的氧化还原化学将大大增加我们对活性金属物种的基本理解，有助于我们了解新的动力学探针的用途，并可能提供对电子结构和计算能力的更深层次的理解。最终，这项工作有望提供机会，实现对氧化催化的详细定量和预测性理解。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the funding from the Chemical Catalysis Program of the Division of Chemistry, Professor John T. Groves of Princeton University and his research group will develop and study catalysts to enable energy-efficient chemical transformations such as C-H activation to better access high added-value chemical products. More than 95% of chemical industry products derive from a small slate of molecular building blocks that are relevant to more than 30% of the GNP of the United States. It is the central thesis of this project that recent conceptual advances in oxidative chemical and biochemical catalysis, and the interplay of emerging experimental techniques and modern theory, offer unprecedented opportunities to develop inexpensive, earth-abundant transition metals as catalysts for these selective processes. The project combines knowledge of biocatalysis used by microorganisms with insights derived from synthetic systems to provide a conceptual basis to understand these processes. Broad application of this chemistry will have high impact on the nation’s and the world’s chemical and energy economies. The Groves group will continue to serve as an effective training ground for graduate students and postdoctoral research associates, especially women and members of under-represented groups in science. In this project, Professor Groves aims to develop new methods for the catalytic oxygenation, fluorination and halogenation of C-H bonds. The development of novel and efficient oxidative processes requires a thorough understanding of the mechanisms of metal-mediated atom transfer by observing the unitary processes of catalysis, also including a range of metal-halogen species, and elucidating the nature of their reactions with organic substrates. In particular, the proposed research strives to elaborate a conceptual basis for heteroatom rebound catalysis, which can be dissected in a manner similar to hydrogen atom transfer. The project will integrate small molecule chemical catalysts with insights from metalloenzymes and biocatalytic processes. Nature employs iron proteins to achieve C-H hydroxylations and halogenations. Through analogy, the redox chemistry of Fe, Mn, Co and other abundant transition metals will add significantly to our fundamental understanding of reactive metal species, of the utility of new kinetic probes, and likely afford a deeper understanding of electronic structure and of the power of computation. In the end, this work is expected to offer opportunities to realize a detailed quantitative and predictive understanding of oxidative catalysis.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.