Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

氧化催化中的金属-氧和金属-过氧中间体

• 批准号: 1148597
• 负责人: John Groves
• 金额: $ 61万
• 依托单位: Princeton University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-04-01 至 2015-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1148597&HistoricalAwards=false
• 关键词: Metal; Oxo; Peroxo; Intermediates; Oxidative

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.

美国国家科学基金会化学部的化学催化项目支持约翰·T·普林斯顿大学的格罗夫斯研究氧化催化。在可预见的未来，碳氢化合物转化将继续在全球能源经济中发挥核心作用。烷烃氧化、水裂解反应和二氧化碳的脱氧都可以设想为涉及氧原子转移。这是该计划的中心论点，最近在氧化催化的概念进展提供了一个前所未有的机会，开发丰富的第一行过渡金属作为这些过程的催化剂。这项研究将结合联合收割机的碳氢化合物化学的巨大水库目前正在实践的好氧和厌氧生物的见解来自合成，仿生系统，以寻找新的催化剂。这种化学的广泛应用可能对国家和世界的化学经济产生巨大影响。该计划的目标是了解和利用涉及金属氧系统的高价过渡金属化学的广度。这一努力的成功可以提供后期药物多样化和代谢物鉴定的新方法，碳氢化合物能量转换的新机会，燃料电池开发的新概念和消毒生物恐怖剂的新工艺。该方法涉及直接的动力学和光谱方法来表征活性，快速催化条件下的活性金属-氧代中间体。一个重要的目标是揭示这些新的催化体系的范围，这些催化体系采用最近发现的氧代和二氧代金属络合物，包括新的C-H卤化方案，重点是基于第一行过渡金属的体系，这些体系具有大规模实施的真实的前景。这项研究的发现将有助于理解化学催化如何运作的基本原理，并将以此推动下一代催化剂的发明，培养国家工业技术进步所需的人才。来自各种背景的学生和博士后研究人员，包括代表性不足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。人类健康受到化学和生物化学催化的选择性的影响，这是制药工业有效生产新的纯药物所必需的。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，使世界经济能够捕获大量的甲烷资源，例如，这些资源现在基本上被浪费了，并使石油原料具有高附加值。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，对于解决这些科学，技术和环境挑战是必要的。