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

合作研究：通过控制 Rh(II) 配合物的轴向配位提高化学选择性和效率：实验和计算方法

• 批准号: 2247836
• 负责人: Dean Tantillo
• 金额: $ 31.23万
• 依托单位: University of California-Davis
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-09-15 至 2026-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247836&HistoricalAwards=false
• 关键词: Collaborative; Research; Enhancing; Chemoselectivity; Efficiency

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.

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和加利福尼亚大学戴维斯分校的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，用于有机转化，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学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。这项研究的更广泛的影响将包括在计算和合成化学的界面上为不同群体的研究生和本科生提供深入的研究培训，从而通过为他们提供一套有价值的研究技能来赋予下一代化学家权力。Darko博士将与当地的诺克斯维尔非营利组织Centro Hispano De East Tennessee合作，为当地社区服务不足的高中生提供机会，在Darko实验室进行原创研究，并了解化学方面的机会和可能的职业。通过计算和实验的努力相结合，这个合作项目旨在揭示新的概念，在dirhodium（II，II）paddlewheel复合物的催化剂控制通过研究远程键合相互作用，涉及催化剂。研究小组将设计一种桥接支架，该支架具有内置配体，能够操纵远端铑位点的反应性。该团队将确定可普遍应用于下一代杂配dirhodium（II，II）桨轮复合物合成的关键参数，增加目前可用类似物的结构多样性。新的二铑配合物将用作金属-卡宾转移化学的催化剂，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。这些研究预计将建立反应的化学选择性的基本趋势时，扰动轴向协调组的dirhodium（II，II）paddlewheel核心。对新复合物的化学选择性概况的理解有望在建立远程协调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NSF的法定使命，并被认为值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估来支持。