Development of Group 9 Transition Metal Catalysts for Hydrocarbon Functionalization

有了这个奖项，化学系的化学催化计划资助教授T。弗吉尼亚大学的布伦特冈诺研究开发催化剂，这种催化剂可以选择性地将碳氢化合物（只含有氢和碳原子的化合物）转化为更复杂的化合物。 来自化石资源的碳氢化合物是化学工业和能源部门的基础。近年来，大量国内天然气储备的使用增加;然而，在当前的技术基础设施下，经济地运输天然气的能力有限，因此美国和世界各地的许多天然气仍然“搁浅”和不可用。此外，尽管经过多年的发展，将烃转化为更高价值的化学品的化学方法通常遭受对所需化合物的低选择性和对高温和高压的要求。因此，用于烷烃官能化的新催化剂对于使用天然气和其他烃作为新化学品和运输燃料的前体是必不可少的。该研究项目还为本科生和研究生提供培训，使未来一代科学家能够在催化领域工作，因为这涉及到化石资源的有效利用。PI还参加了由弗吉尼亚大学的“超过分数”项目、达登商学院和“未来汽车峰会”主办的几次外展和研讨会活动。“Gunnoe教授正在合成和研究第9族过渡金属络合物，用于烃的催化功能化。该项目建立在Gunnoe小组的初步工作的基础上，该工作证明了新型铑络合物在酸性条件下激活烃的碳氢键的能力。这些结果被扩展到所需的催化循环中的所有步骤的详细研究，包括碳氢活化步骤（芳烃和烷烃），过渡金属烃基络合物的氧化，和金属-烃基配体的还原官能化。在酸性介质中的反应是目标，产生氧官能化的化合物，如酯。一个目的是寻求理解如何合理地设计基于钴、铑和铱的催化剂以优化酸性溶剂中的碳氢活化速率。第二个推力寻求开发和理解在酸性溶剂中还原官能化的优化。第三个目的是将这些单独的步骤组合成用于氧化烃官能化的催化方法。

With this award, the Chemical Catalysis Program of the Chemistry Division is funding Professor T. Brent Gunnoe of the University of Virginia to study the development of catalysts that can selectively convert hydrocarbons, compounds that only contain hydrogen and carbon atoms, into more complex compounds. Hydrocarbons from fossil resources form the foundation of the chemical industry and the energy sector. Recent years have seen an increase in access to vast amounts of domestic natural gas reserves; however, with current technological infrastructure the ability to transport natural gas economically is limited and therefore much natural gas in the U.S. and around the world remains "stranded" and unusable. Also, despite years of development, chemical processes that convert hydrocarbons into higher value chemicals often suffer from low selectivity for a desired compound and the requirement of high temperatures and pressures. Thus, new catalysts for alkane functionalization are essential for use of natural gas, and other hydrocarbons, as a precursor to new chemicals and transportation fuel. This research project is also providing training to undergraduate and graduate students to enable a future generation of scientists to work in the area of catalysis as it relates to the efficient use of fossil resources. The PI has also participated in several outreach and workshop events hosted by the University of Virginia's "More Than the Score" program, the Darden School of Business, and the "Car of the Future Summit."Professor Gunnoe is synthesizing and studying group 9 transition metal complexes for the catalytic functionalization of hydrocarbons. This project builds on preliminary work in the Gunnoe group that demonstrated the ability of novel rhodium complexes to activate the carbon-hydrogen bonds of hydrocarbons under acidic conditions. These results are being extended to a detailed study of all steps in the desired catalytic cycles, including the carbon-hydrogen activation step (both arenes and alkanes), oxidation of the transition metal hydrocarbyl complex, and reductive functionalization of the metal-hydrocarbyl ligand. Reactions in acidic media are being targeted that yield oxy-functionalized compounds such as esters. One objective seeks to understand how to rationally design catalysts based upon cobalt, rhodium and iridium to optimize the rate of carbon-hydrogen activation in acidic solvent. A second thrust seeks to develop and understand optimization of reductive functionalization in acidic solvent. The third objective combines these individual steps into catalytic processes for oxidative hydrocarbon functionalization.