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

在这个由化学系化学结构、动力学机制B计划资助的CAREER项目中，美国圣母大学化学与生物化学系的艾米丽·徐教授正在研究一类新的过渡金属硫配合物。 这项研究的目标是利用这些配合物开发新的催化反应，并作为储存能量或电力的新方法。 该项目将支持对研究生和本科生的培训，使他们做好准备，成为科学劳动力的成功成员。此外，我们亦会制作更多教育外展材料，以提高中学生及其家长和教师的科学参与度，特别是在可再生能源方面。徐教授及其研究小组现正研究将元素硫插入第一行过渡金属硫醇化合物中，以形成金属多硫酰复合物。合成，光谱和电化学研究将进行这些配合物，以探测多硫基形成和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，然后被用于设计新的催化剂的硫转移反应的不饱和有机底物。 此外，Tsui团队的目标是开发新的方法来控制硫还原时多硫化物离子的形态。 本研究的具体目标有三：（1）元素硫被金属硫醇盐螯合物和非螯合物活化;（2）Tsui研究小组的目标是开发由金属多硫基络合物介导的催化碳硫键形成反应，以及（3）Notre Dame团队计划研究金属多硫酰复合物的氧化还原特性。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知识价值和更广泛的影响审查标准进行评估。

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.