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计划资助的项目中，Macalester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了用于化学合成应用的新的Re(Re)金属配合物。具体地说，目标稀土配合物有望与有机分子(例如，苯和萘，原油中发现的廉价物质)结合，并在温和的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品转化为更有用的物质，这些物质需要更多的能源密集型战略来使用目前的方法进行准备。该项目将为包括女性和非裔美国学生在内的有才华的本科生提供一个激动人心的现代研究方法培训基地。这项研究计划旨在使本科生具备技能、坚韧和热情，以便在后续的研究生学习中促进他们在化学研究中的成功。本项目考察了使用三(膦)硼酸盐作为氢三(1-吡唑基)硼酸盐的替代品来制备具有高倾向配位芳烃的pi-碱性片段的可行性和优势。人们正在进行热合成和光化学合成，以开辟三(膦)硼酸Re化学这一完全未被探索的领域。特别强调调节三(膦)硼酸盐Re碎片的电子和空间环境，以实现芳香族底物的最佳脱芳构化。反应产物用核磁共振和红外光谱、循环伏安法和X射线结晶学进行了表征，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.