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，北达科他州州立大学的赵品晶博士正在研究用于有机分子合成的金属基催化剂。金属催化剂，加速反应的分子，必须与目标起始材料（底物）相互作用，以将反应物转化为产物。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，为环境友好的化学合成提供新工具。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。在大二有机化学讲座课程中介绍了催化反应和合成反应。学生项目是为无机实验室课程开发的，以提供仪器和实验室技术的实践经验。赵教授领导建立了一个基于网络的数据库，以促进金属有机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了宝贵的培训经验，培训他们在工业，政府和学术界的职业生涯。赵博士正在开发基于后过渡金属的环化过程的催化应用。催化相关的金属杂环是通过镍和铼介导的辅助配体如N-杂环卡宾（NHC）和芳族N-H酮亚胺的C-H键活化产生的。其他靶环化过程包括铑和铑离子介导的芳烃羧酸和杂芳烃羧酸通过螯合辅助的脱羧。环化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活化强化学键（包括碳-氢、氧-氢和碳-碳键）来指导新的催化剂开发。赵博士还领导了一项计划，开发一个基于网络的可搜索数据库，以促进有机金属化学中化学键转化基础知识的普遍传播。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值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.