Understanding and Directing the Reactivity of Cyclometalated Complexes in Late Transition Metal-Based Homogeneous Catalysis

在化学系化学催化项目的资助下，北达科他州立大学法戈分校的赵品静博士正在研究用于合成有机分子的金属催化剂。金属催化剂是加速反应的分子，必须与目标起始材料(底物)相互作用，才能将反应物转化为产品。赵博士正在研究新催化剂的合理设计和开发，包括那些不使用昂贵和稀有金属的催化剂，为环境友好型化学合成提供新的工具。该项目为研究生和本科生提供跨学科的研究培训和职业准备。在二年级的有机化学课程中介绍了催化和合成反应。学生专题是为无机实验课程开发的，以提供仪器和实验技术的实践经验。赵教授领导建立了一个基于网络的数据库，以促进有机金属化学基础知识和最新研究进展的广泛传播。该数据库为研究生和本科生提供宝贵的培训经验，为他们在工业、政府和学术界的职业生涯进行培训。赵博士正在开发基于后过渡金属的环金属化过程的催化应用。N-杂环卡宾(NHCS)和芳香族N-H-酮胺等辅助配体通过镍和Ru介导的C-H键活化生成催化相关的金属环。其他目标环金属化过程包括通过螯合辅助进行的由Rh和Ru介导的芳烃和杂芳烃羧酸的脱羧化反应。环金属催化剂前体和活性中间体的结构-反应性关系的结果通过原子有效地激活包括碳-氢、氧-氢和碳-碳键在内的强化学键来指导新催化剂的开发。赵博士还领导了一项基于网络的可搜索数据库的开发计划，以促进有机金属化学中化学键转化基础知识的广泛传播。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。

With funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. Pinjing Zhao of North Dakota State University Fargo is studying metal-based catalysts for the synthesis of organic molecules. Metal catalysts, molecules that speed up reactions, must interact with the target starting materials (substrates) in order to transform the reactants into products. Dr. Zhao is studying the rational design and development of new catalysts, including those that do not employ expensive and rare metals, to provide new tools for environmentally-friendly chemical synthesis. This project provides interdisciplinary research training and career preparation for graduate and undergraduate students. Catalytic and synthetic reactions are introduced in the sophomore organic chemistry lecture course. Student projects are developed for the inorganic laboratory course to provide hands-on experience with instrumentation and lab techniques. Professor Zhao leads the construction of a web-based database to promote general dissemination of the fundamental knowledge and recent research progress on organometallic chemistry. This database provides valuable training experiences for graduate and undergraduate students training them for careers in industry, government and academia. Dr. Zhao is developing catalytic applications of late transition metal-based cyclometalation processes. Catalytically-relevant metallacycles are generated through nickel- and ruthenium-mediated C-H bond activation of ancillary ligands such as N-heterocyclic carbenes (NHCs) and aromatic N-H ketimines. Other target cyclometalation processes include rhodium- and ruthenium-mediated decarboxylation of arene- and heteroarenecarboxylic acids via chelation assistance. Results of structure-reactivity relationships of cyclometalated catalyst precursors and reactive intermediates are guiding new catalyst developments via atom-efficient activation of strong chemical bonds including carbon-hydrogen, oxygen-hydrogen, and carbon-carbon bonds. Dr. Zhao is also leading an initiative to develop a web-based searchable database to promote general dissemination of fundamental knowledge on chemical bond transformations in organometallic chemistry.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.