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

在化学系化学合成项目的支持下，乔治亚南方大学阿姆斯特朗校区化学与生物化学系的Brandon Quillian教授将进行一个基础研究项目，开发过渡金属基催化剂，该催化剂能够将相当惰性的石油资源转化为增值产品，与现代方法相比，采用“更环保”的方法。但通常存在多种缺陷，如反应温度高、非选择性、大量废物流和无法回收催化剂。这些有针对性的、高价值的、工业上重要的产品目前每年以多吨的规模生产，用于制造塑料、药品和洗涤剂。借鉴之前在这方面的研究进展，研究者的目标是为化学界提供新的知识，进一步提高我们对这类系统的理解，这些系统可能会导致更有效的过程，从而保护石油资源。该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研究者的直接指导。这些学生将接受最先进的方法、技术和仪器的培训，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，由于佐治亚南方大学的丰富多样性和研究者热心致力于指导这些学生为他们在科学领域的职业生涯做好准备，该项目预计将对代表性不足的少数民族产生直接影响。该项目涉及基础研究，旨在开发明确的、均相的、由双齿供体配体（联吡啶衍生物）和其他支持配体（不稳定和辅助配体）支持的钌（II）烯烃氢芳基化催化剂。这些催化剂通过金属介导的C- h活化将非活化烯烃和芳烃偶联，随后通过插入烯烃实现功能化，促进芳基C- h键在烯烃C=C键上加成，生成烷基烯。所提出的催化剂是高度模块化和易于制备，允许系统的改变系统，以优化催化。为了更好地了解催化烯烃氢化反应体系，我们将对几种催化剂变体进行立体构型和电子学的构效关系研究。反应的底物范围将使用具有吸电子和供电子基团的各种芳烃以及环烯烃和高取代烯烃来测定。这些研究的产物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，气相和液相色谱，循环伏安法和单晶x射线衍射。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的理解，以及什么构成了可行催化的必要特征，以及通过代理，系统的空间和电子极限。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值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.