RUI: CAS: Development of New Octahedral Ruthenium(II) Olefin Hydroarylation Catalysts Supported by a Single Bidentate Support Ligand

在化学系化学合成计划的支持下，佐治亚州南部大学阿姆斯特朗校区化学和生物化学系的Brandon Quillian教授将继续进行一个基础研究项目，以开发过渡金属催化剂，与当代方法相比，这种催化剂能够以更环保的方法将相当惰性的石油资源转化为附加值产品。当代方法往往存在反应温度高、非选择性、大量废物和无法回收催化剂等多重缺陷。这些目标明确、价值极高、具有工业重要性的产品目前每年以数吨规模生产，用于制造塑料、药品和洗涤剂。借鉴这一研究领域以前的进展，研究人员旨在向化学界提供新的知识，以进一步提高我们对这些类型的系统的理解，这些系统可能会导致更有效的过程，从而保护石油资源。这个项目将支持两名本科生的研究活动，他们将受益于经验丰富的调查员的直接指导。这些学生将接受最先进的方法、技术和乐器方面的培训，并培养在未来就业中取得成功所需的软技能。这种培训对于将这些学生培养成研究科学家是不可或缺的，以支持对合格的科学、技术、工程和数学(STEM)毕业生日益增长的需求。此外，由于南乔治亚大学具有丰富的多样性，而且调查员热切致力于指导这些学生为从事科学事业做准备，预计该项目将对代表性不足的少数群体产生立竿见影的影响。该项目涉及基础研究，旨在开发由双齿配体(联吡啶衍生物)和其他支撑配体(不稳定配体和辅助配体)支撑的定义明确、均一的Ru(II)烯烃氢芳基化催化剂。这些催化剂有望通过金属介导的C-H活化将未活化的烯烃和芳烃偶联，然后通过插入烯烃来促进芳基C-H键在烯烃C=C键上的加成，从而生成烷基芳烃。所建议的催化剂是高度模块化的，易于制备，允许系统地改变系统以优化催化。为了更好地了解该体系，我们将对几种催化剂上的催化烯烃氢芳化反应的构效关系进行研究。反应的底物范围将使用各种芳烃进行测量，这些芳烃既有吸电子基团，也有给电子基，以及环状和高度取代的烯烃。这些研究的产品和中间体将使用现代光谱方法进行表征，如核磁共振和红外光谱以及质谱仪、气相色谱和液相色谱、循环伏安法和单晶X射线衍射法。预计这项研究的结果将增加对如何最好地合成这些类型的系统以及什么构成可行催化的必要特征以及系统的空间和电子极限的理解。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 support of the Chemical Synthesis program in the Division of Chemistry, Professor Brandon Quillian of the Department of Chemistry and Biochemistry, Georgia Southern University-Armstrong Campus will pursue a project in fundamental research to develop transition metal-based catalysts capable of converting fairly inert petroleum resources into value-added products by a “greener” method as compared to contemporary methods, which often suffer from multiple deficiencies such as high reaction temperatures, non-selectivity, large waste streams and the inability to recover catalysts. The targeted, highly valued, industrially important products are currently produced yearly on multi-ton scales for the manufacture of plastics, medicines and detergents. Borrowing from previous advances in this vein of research, the investigator aims to provide new knowledge to the chemistry community to further improve our understanding of these types of systems that may lead to more efficient processes, thereby preserving petroleum resources. This project will support the research activities of two undergraduate students who will benefit from direct supervision from the experienced investigator. These students will be trained in the state-of-art methods, techniques, and instrumentation, as well as build soft skills required to be successful in their future employment. This training is integral to developing these students into research scientists to support the increasing need for qualified science, technology, engineering, and mathematics (STEM) graduates. Moreover, this project is expected to have an immediate impact on underrepresented minorities due to the rich diversity of Georgia Southern University and the investigator’s ardent commitment to mentoring these students to prepare them for careers in the sciences. The project deals with fundamental research aimed at developing well-defined, homogenous, ruthenium(II) olefin hydroarylation catalysts supported by a bidentate donor ligand (bipyridine derivatives) and other support ligands (labile and ancillary ligands). These catalysts are expected to couple non-activated olefins and arenes using metal-mediated C-H activation and subsequent functionalization through olefin insertion to facilitate the addition of aryl C-H bonds across olefin C=C bonds to produce alkylarenes. The proposed catalysts are highly modular and easy to prepare, allowing for systematic alteration of the system to optimize catalysis. A catalytic olefin hydroarylation structural-activity relationship study will be performed as a function of sterics and electronics on several catalyst variants to gain a better understanding of the system. The substrate scope of the reaction will be gauged using various arenes with both electron-withdrawing and electron-donating groups, and cyclic and highly substituted olefins. The products and intermediates of these studies will be characterized using modern spectroscopic methods such as nuclear magnetic resonance and infrared spectroscopy as well as mass spectrometry, gas and liquid chromatography, cyclic voltammetry, and single crystal X-ray diffraction. It is expected that the outcomes of this study will increase understanding on how to best synthesize these types of systems and what constitutes the necessary features for viable catalysis, and by proxy, the steric and electronic limits of the system.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.