CAREER: CAS: Organometallic Chemistry of Catalytically Relevant Copper(III) Complexes

职业：CAS：催化相关铜 (III) 配合物的有机金属化学

• 批准号: 2237757
• 负责人: Wei Liu
• 金额: $ 77万
• 依托单位: University of Cincinnati Main Campus
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-04-01 至 2028-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2237757&HistoricalAwards=false
• 关键词: CAREER; CAS; Organometallic; Chemistry; Catalytically

In this CAREER project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Wei Liu of the Department of Chemistry at University of Cincinnati is studying the fundamental reactivity of copper complexes for synthesizing important organic molecules. Compared to the precious metal analogues, copper catalysts are less expensive, less toxic, and have higher abundancy in the earth’s crust. However, the catalytic performance of copper complexes lags largely behind that of their precious metal counterparts, largely owing to limited understanding of the fundamental reactivity of copper complexes. The goal of this research is to study the reactivity of copper complexes that are plausible intermediates in catalytic Cu-mediated bond construction reactions. Investigations of the structure and reactivity of these complexes is directed at providing a deeper mechanistic understanding of known copper-catalyzed bond-forming reactions, enabling the development of improved copper catalysts, and inspiring the development of new copper-catalyzed transformations. Dr. Liu’s education plan focuses on increasing public awareness of the importance of organic chemistry in daily life and on the retention of underrepresented minorities in science through outreach programs at the Cincinnati Museum Center, research-based educational experiences, and online resources.High-valent organo-Cu(III) compounds have long been proposed as key intermediates in many Cu-catalyzed transformations. However, most reported examples of isolated Cu(III) species are stabilized by rigid macrocyclic chelating or perfluorinated ligands, and few of these examples provide experimental evidence for elemental reactions in Cu catalysis. In this project, the Liu research team will investigate the synthetic accessibility of reactive organo-Cu(III) compounds, study the elementary reactions of well-defined Cu(III) species, explore the structure of catalytically relevant Cu(III) complexes, and work to exploit their reactivity to discover new Cu-catalyzed transformations. An improved fundamental understanding of the reactivity of Cu(III) compounds, including homolytic dissociation, reductive elimination, and oxidative addition, would not only provide insights into existing reactions that involve Cu(III) intermediates but also inspire the development of novel Cu-catalyzed transformations.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.

在这个由化学系化学结构、动力学和机理B项目资助的CAREER项目中，辛辛那提大学化学系的Wei Liu正在研究铜配合物合成重要有机分子的基本反应性。与金属类似物相比，铜催化剂价格便宜，毒性较小，并且在地壳中含量较高，但铜配合物的催化性能很大程度上落后于贵金属。盟友，主要是由于对铜配合物的基本反应性的了解有限，本研究的目的是研究铜配合物的反应性，这些铜配合物是催化铜介导的键构建反应的结构和反应性的研究。旨在提供对已知的铜催化成键反应的更深入的机理理解，促进改进的铜催化剂的开发，并激发新的铜催化转化的发展。刘博士的教育计划侧重于增加公众的参与。通过辛辛那提博物馆中心的外展计划、基于研究的教育经验和在线资源，人们认识到有机化学在日常生活中的重要性，以及保留科学界中代表性不足的少数群体。高价有机铜（III）化合物长期以来已被提议作为许多 Cu 催化转化的关键中间体，然而，大多数报道的分离 Cu(III) 物质的例子是通过刚性大环螯合或全氟化配体来稳定的，并且这些例子中很少有为 Cu 催化中的元素反应提供实验证据。在这个项目中，刘研究小组将研究反应性有机Cu(III)化合物的合成可及性，研究明确定义的Cu(III)物种的基元反应，探索催化相关的Cu(III)配合物的结构，以及致力于利用它们的反应性来发现新的 Cu 催化转化，提高对 Cu(III) 化合物反应性的基本了解，包括均解离解、还原消除和氧化加成，不仅可以提供对涉及的现有反应的见解。 Cu(III) 中间体，而且还激发了新型铜催化转化的发展。该奖项反映了 NSF 的法定使命，并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，被认为值得支持。

项目成果

Copper–Carbon Homolysis Competes with Reductive Elimination in Well-Defined Copper(III) Complexes

在明确的铜 (III) 配合物中，铜碳均质作用与还原消除竞争

• DOI: 10.1021/jacs.3c08510
• 发表时间: 2023-12
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Yan, Wenhao;Carter, Samantha;Hsieh, Chi;Krause, Jeanette A.;Cheng, Mu;Zhang, Shiyu;Liu, Wei
• 通讯作者: Liu, Wei