CAREER: Formation and Redox Chemistry of Metal Polysulfanido Complexes for Sulfur Transfer Reactions

美国圣母大学化学与生物化学系的Emily Tsui教授正在研究一类新的过渡金属硫配合物，该项目由化学学部化学结构、动力学与机理B项目资助。这项研究的目标是利用这些配合物来开发新的催化反应，并作为储存能量或电力的新方法。该项目将支持研究生和本科生的培训，使他们成为科学队伍的成功成员。将编写更多的教育推广材料，以提高中学生及其家长和教师的科学参与，特别是在可再生能源领域。Tsui教授和她的团队正在研究通过在第一排过渡金属硫酸盐化合物中插入单质硫来形成金属多磺胺配合物。将对这些配合物进行合成、光谱和电化学研究，以探索多磺胺形成与配体环应变或取代之间的关系。从这些研究中收集到的见解将用于设计新的催化剂，用于硫转移反应到不饱和有机底物。此外，Tsui团队的目标是开发新的方法来控制硫还原过程中多硫离子的形态。研究的三个具体目标是：(1)元素硫被金属硫酸盐螯合物和非螯合物激活；(2) Tsui研究小组的目标是开发由金属聚磺胺配合物介导的催化碳-硫键形成反应；(3)Notre Dame研究小组计划研究金属聚磺胺配合物的氧化还原性能。该奖项反映了美国国家科学基金会的法定使命，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。

In this CAREER project, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Emily Tsui of the Department of Chemistry and Biochemistry at the University of Notre Dame is studying a new class of transition metal sulfur complexes. The goal of this research is to use these complexes for the development of new catalytic reactions and as new ways to store energy or electricity. This project will support the training of graduate and undergraduate students to prepare them to become successful members of the scientific workforce. Additional educational outreach materials are to be developed to improve the scientific engagement of middle school students and their parents and teachers, particularly in the area of renewable energy.Professor Tsui and her group are studying the formation of metal polysulfanido complexes via the insertion of elemental sulfur into first-row transition metal thiolate compounds. Synthetic, spectroscopic, and electrochemical studies will be carried out on these complexes to probe the relationship between polysulfanido formation and ligand ring strain or substitution. Insights gleaned from these studies are then to be used in the design of new catalysts for sulfur transfer reactions to unsaturated organic substrates. Additionally, the Tsui team aims to develop new ways of controlling the speciation of polysulfide ions upon sulfur reduction. There are three specific aims of the research to be undertaken: (1) Elemental sulfur is to be activated by metal thiolate chelate and nonchelated complexes; (2) The Tsui research team aims to develop catalytic carbon-sulfur bond-forming reactions mediated by metal polysulfanido complexes and (3) The Notre Dame team plans to study the redox properties of metal polysulfanido complexes.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.