Collaborative Research: Enhancing Chemoselectivity and Efficiency Through Control of Axial Coordination in Rh(II) Complexes: An Experimental and Computational Approach

在化学系化学合成项目的支持下，田纳西大学诺克斯维尔分校的Ampofo Darko和加州大学戴维斯分校的Dean Tantillo将研究和开发新的方法，以提高铑基催化剂的效率和功能，从而产生难以生产的化合物。研究团队将利用他们在实验合成方法和计算化学方面的综合优势来探索决定化学反应结果的因素，并将使用生成的数据来指导这些铑基催化剂的进一步开发，以用于更具挑战性的反应。这项研究的广泛影响将包括为计算化学和合成化学领域的研究生和本科生提供深入的研究培训，从而通过为下一代化学家提供一套有价值的研究技能来增强他们的能力。达科博士将与诺克斯维尔当地的非营利机构东田纳西州中心合作，为当地社区服务不足的高中学生提供一个机会，让他们在达科实验室从事原创研究，并了解化学领域的机会和可能的职业。通过计算和实验相结合的努力，该合作项目旨在通过研究涉及催化剂的远程键合作用，揭示镉（II，II）桨轮配合物中催化剂控制的新概念。研究小组将设计一种桥接支架，其内置配体能够操纵远端铑位点的反应性。该团队将确定关键参数，这些参数可以普遍应用于合成下一代异电性镝（II，II）桨轮配合物，增加目前可用类似物的结构多样性。新的钯配合物将被用作金属-碳烯转移化学的催化剂，重点是探索远程相互作用对环丙烷化或芳烃插入反应的催化剂效率和选择性的影响。这些研究有望在干扰（II，II）桨轮核心上的轴向配位基时，建立反应化学选择性的基本趋势。对新配合物的化学选择性特征的了解有望在建立远程配位在复杂有机分子合成中的作用方面产生丰富的红利。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, Ampofo Darko of the University of Tennessee-Knoxville and Dean Tantillo of the University of California-Davis, will study and develop new methodology to improve the efficiency and function of rhodium-based catalysts for organic transformations that result in the generation of difficult-to-produce compounds. The research team will utilize their combined strengths in experimental synthesis methodology and computational chemistry to probe factors that determine the outcomes of the chemical reactions, and will use the generated data to guide the further development of these rhodium-based catalysts for more challenging reactions. The broader impacts of this research will include providing in-depth research training for a diverse group of graduate and undergraduate students at the interface of computational and synthetic chemistry, thereby empowering the next generation of chemists by equipping them with a valuable set of research skills. Dr. Darko will partner with local Knoxville non-profit Centro Hispano De East Tennessee to provide an opportunity for underserved high school students in the local community to work on original research in the Darko lab and learn about opportunities and possible careers in chemistry. Through a combination of computational and experimental efforts, this collaborative project seeks to uncover new concepts in catalyst control in dirhodium(II,II) paddlewheel complexes by studying remote bonding interactions involving the catalyst. The research team will design a bridging scaffold that has built-in ligands that are capable of manipulating reactivity from the distal rhodium site. The team will identify key parameters that can be applied generally to the syntheses of next-generation heteroleptic dirhodium(II,II) paddlewheel complexes, adding to the structural diversity of currently available analogues. The new dirhodium complexes will be employed as catalysts for metal-carbene transfer chemistry, with an emphasis on probing the effect of remote interactions on catalyst efficiency and selectivity for cyclopropanation or arene insertion reactions. These studies are expected to establish fundamental trends in reaction chemoselectivity when perturbing axial coordinating groups on the dirhodium(II,II) paddlewheel core. An understanding of the chemoselectivity profile of the new complexes is expected to yield rich dividends in establishing the role of remote coordination in the synthesis of complex organic molecules.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.