RUI: An Examination of the Utility of Tris(phosphino)borates as Supporting Ligands for Rhenium(I) Dihapto-Arene Complexes

在这个由化学系化学合成项目资助的项目中，麦卡莱斯特学院的Paul J. Fischer教授带领一个专门由本科生组成的研究小组，设计和合成用于化学合成的新型铼（Re）金属配合物。具体来说，目标Re配合物预计会结合有机分子（例如，苯和萘，原油中发现的廉价物质），并在温和条件下激活它们进行反应。这些反应的假设结果包括将这些丰富的原料化学物质转化为更有用的物质，这需要使用当前方法进行制备的能源密集型策略显著增加。该项目将为有才华的本科生，包括女性和非洲裔美国学生，提供一个令人振奋的现代研究方法训练基地。该研究项目旨在为本科生提供技能、毅力和热情，以促进他们在随后的研究生学习中在化学研究方面取得成功。本项目探讨了采用三（膦）硼酸盐作为三（1-吡唑基）硼酸盐的替代品，制备具有高倾向于以二hapto方式配位芳烃的pi碱性片段的可行性和优点。热和光化学合成正在进行，以打开三（膦）硼酸铼化学完全未开发的领域。特别强调的是调节三（膦）硼酸盐的Re片段的电子和空间环境，以实现芳香底物的最佳脱芳。反应产物通过NMR（核磁共振）和IR（红外）光谱，循环伏安法和x射线晶体学进行表征，后者是与明尼苏达大学合作进行的。

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Paul J. Fischer of Macalester College leads a research group of exclusively undergraduate students in designing and synthesizing new rhenium (Re) metal complexes for chemical synthesis applications. Specifically, the target Re complexes are anticipated to bind organic molecules (for example, benzene and naphthalene, inexpensive substances found in crude petroleum), and activate them toward reactions under mild conditions. The hypothesized results of these reactions include transformations of these abundant feedstock chemicals into more useful substances that require significantly more energy-intensive strategies to prepare using current methods. This project will provide a stimulating training ground in modern research methods for talented undergraduate students including women and African American students. This research program seeks to equip undergraduate students with the skills, tenacity and enthusiasm to facilitate their success in chemical research in subsequent graduate studies.This project examines the feasibility and advantages of employing tris(phosphino)borates as surrogates for hydrotris(1-pyrazolyl)borate for the preparation of pi-basic fragments with high propensity to coordinate arenes in a dihapto fashion. Thermal and photochemical syntheses are being pursued to open the completely unexplored area of tris(phosphino)borate rhenium chemistry. Special emphasis is being placed on modulating the electronic and steric environment of Re fragments of tris(phosphino)borates for optimum dearomatization of aromatic substrates. Reaction products are characterized by NMR (nuclear magnetic resonance) and IR (infra-red) spectroscopies, cyclic voltammetry and X-ray crystallography, the latter via collaboration with the University of Minnesota.