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

在这个由化学部化学结构、动力学机制B计划资助的CAREER项目中，辛辛那提大学化学系的刘伟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，铜催化剂更便宜，毒性更小，并且在地壳中具有更高的abbits。然而，铜配合物的催化性能大大落后于其贵金属对应物，这主要是由于对铜配合物的基本反应性的理解有限。本研究的目的是研究铜配合物的反应性，这些配合物是催化铜介导的键构建反应中可能的中间体。这些配合物的结构和反应性的调查是针对提供一个更深的机制的理解已知的铜催化的键形成反应，使改进的铜催化剂的发展，并激发新的铜催化转化的发展。 刘博士的教育计划侧重于提高公众对有机化学在日常生活中的重要性的认识，并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，保留在科学中代表性不足的少数民族。高价有机铜（III）化合物长期以来一直被认为是许多铜催化转化的关键中间体。然而，大多数报道的孤立的Cu（III）物种的例子是稳定的刚性大环螯合或全氟化配体，这些例子中很少有提供实验证据的Cu催化元素反应。在这个项目中，Liu研究团队将研究反应性有机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Cu（III）络合物的结构，并努力利用它们的反应性来发现新的Cu催化转化。对Cu（III）化合物的反应性，包括均裂解离、还原消除和氧化加成，不仅提供了对涉及Cu（III）中间体的现有反应的深入了解，而且还激发了新型Cu-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。

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.