Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

国家科学基金会化学部的化学催化计划支持普林斯顿大学的约翰·T·格罗夫斯教授对氧化催化的研究。在可预见的未来，碳氢化合物转换将继续在全球能源经济中发挥核心作用。可以预见，烷烃氧化、水分解反应和二氧化碳的脱氧都涉及氧原子转移。该计划的中心论题是，氧化催化的最新概念进展为开发丰富的第一排过渡金属作为这些过程的催化剂提供了前所未有的机会。这项研究将把好氧和厌氧生物目前正在实践的巨大碳氢化合物化学储藏库的知识与来自合成仿生系统的见解结合起来，以寻找新的催化剂。这种化学的广泛应用可能会对国家和世界的化学经济产生巨大影响。这个项目的目标是理解和利用涉及金属氧合体系的高价过渡金属化学的广度。这一努力的成功可能会为后期药物多样化和代谢物鉴定提供新的方法，为碳氢化合物的能量转换提供新的机会，为燃料电池的开发提供新的概念，并为消毒生物恐怖分子提供新的工艺。该方法包括直接动力学和光谱方法来表征活性金属氧代中间体在活性、快速催化条件下的特征。一个重要的目标是揭示这些新的催化系统的范围，这些新的催化系统使用最近发现的进入氧和二氧化氧金属络合物的物质，包括新的C-H卤化协议，重点是具有大规模实施前景的第一排过渡金属系统。这项研究的发现将有助于理解化学催化如何工作的基本原理，并将利用这些见解来推动下一代催化剂的发明，并培训国家实现工业技术进步所需的人员。来自不同背景的学生和博士后研究助理，包括未被充分代表的少数民族化学家以及一些本科生将在实验室接受培训。化学催化是国家和世界经济健康的核心，美国约30%的GNP和至少80%的化学工业依赖于催化过程。因此，化学工业是美国训练有素的科学家的主要雇主。化学和生化催化的选择性对人类健康有影响，而化学和生化催化是制药工业高效生产新药物和纯药物所必需的。在过去的三年里，已经申请了四项专利，并成立了一家新公司，将这一项目和相关项目的进展商业化，特别是在药物发现领域。还需要新的技术，以使世界经济能够捕获大量的甲烷资源，例如，甲烷现在基本上被浪费了，并为石油原料提供高附加值。特别是在氧化催化方面的新发现，这是本文所述拟议研究的核心活动，对于应对这些科学、技术和环境挑战是必要的。

The Chemical Catalysis Program in the Chemistry Division at the National Science Foundation supports Professor John T. Groves of Princeton University for studies of oxidative catalysis. Hydrocarbon transformations will continue to play central roles in the global energy economy into the foreseeable future. Alkane oxygenations, water splitting reactions and the deoxygenation of carbon dioxide all can be envisioned to involve oxygen atom transfers. It is the central thesis of this program that recent conceptual advances in oxidative catalysis offer an unprecedented opportunity to develop abundant first-row transition metals as catalysts of these processes. The research will combine knowledge of the huge reservoir of hydrocarbon chemistry currently being practiced by aerobic and anaerobic organisms with insights derived from synthetic, biomimetic systems to find new catalysts. Broad application of this chemistry could have tremendous impact on the nation's and the world's chemical economy. The goal of this program is to understand and harness the breadth of high-valent transition metal chemistry involving metal oxo systems. Success in this endeavor could offer new methods of late-stage drug diversification and metabolite identification, new opportunities for energy transduction with hydrocarbons, new concepts for the development of fuel cells and new processes for disinfecting bioterrorism agents. The approach involves direct kinetic and spectroscopic methods to characterize reactive metal-oxo intermediates under conditions of active, fast catalysis. An important goal is to reveal the range of these new catalytic systems that employ recently-discovered entries into oxo- and dioxo-metal complexes, including new C-H halogenation protocols, with a focus on first-row transition metal based systems that have real prospects of being implemented on a massive scale.Discoveries from this research will help understand the basic principles of how chemical catalysis operates, and will use such insights to drive the invention of the next generation of catalysts and to train the personnel that are necessary for the nation to achieve technological advances in industry. Students and postdoctoral research associates from a variety of backgrounds and including underrepresented minority chemists as well as a number of undergraduates will be trained in the laboratory. Chemical catalysis is central to the economic health of the nation and the world with about 30% of the GNP of the United States and at least 80% of the chemical industry dependent upon catalytic processes. As a result the chemical industry is a major employer of US trained scientists. Human health is impacted by the selectivity of chemical and biochemical catalysis that is necessary for the pharmaceutical industry to produce new and pure drugs efficiently. Four patents have been filed over the past three years and a new company has been founded to commercialize advances from this and related projects, especially in the area of drug discovery. New technologies are also needed to allow the world economy to capture the vast resources of methane, for example, which are now largely wasted, and to give high value added to petroleum feedstock. New discoveries in oxidative catalysis in particular, which is the core activity of the proposed research described herein, are necessary to address these scientific, technological and environmental challenges.