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

在这个由化学系化学结构、动力学和机理B计划资助的职业项目中，辛辛那提大学化学系的刘伟(音译)正在研究铜配合物合成重要有机分子的基本反应性。与贵金属类似物相比，铜催化剂价格更低，毒性更小，在地壳中的丰度更高。然而，铜配合物的催化性能在很大程度上落后于它们的贵金属同行，这在很大程度上是因为人们对铜配合物的基本反应活性的了解有限。本研究的目的是研究在催化铜介导键构建反应中作为可能的中间体的铜配合物的反应性。对这些配合物的结构和反应活性的研究旨在提供对已知的铜催化成键反应的更深层次的机理理解，使改进的铜催化剂的开发成为可能，并激励新的铜催化转化的发展。刘博士的教育计划侧重于通过辛辛那提博物馆中心的推广计划、基于研究的教育经验和在线资源，提高公众对有机化学在日常生活中的重要性的认识，以及通过在科学中保留代表性较低的少数族裔的重要性。长期以来，高价有机铜(III)化合物一直被认为是许多铜催化转化的关键中间体。然而，大多数报道的孤立铜(III)物种的例子都是通过刚性大环螯合或全氟化配体来稳定的，这些例子很少能为铜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铜(III)化合物的合成可及性，研究明确定义的铜(III)物种的基本反应，探索催化相关的铜(III)配合物的结构，并努力利用它们的反应性来发现新的铜催化转化。提高对铜(III)化合物的反应性的基本了解，包括均解解离、还原消除和氧化加成，不仅将提供对涉及铜(III)中间体的现有反应的见解，还将激励新的铜催化转化的发展。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.