Systematic Metallaborane Reaction Chemistry

圣母大学化学系Thomas P.Fehlner博士得到化学部无机、生物无机和有机金属计划的支持，以合成同时包含主基和过渡金属原子的新原子簇。该项目有几个重点领域。第一个涉及对低电子金属硼烷电子结构的实验和理论评估，低电子金属硼烷是一组6、7和8族金属的金属硼烷，表现出与其他多面体硼烷和金属原子簇不同的高度凝聚结构，并且不遵循Wade规则。其次，金属硼烷将被用来修饰有机底物，其中B-H和M-H片段的特征反应性在单一结合的有机底物上顺序操作，从而产生新的湿法金属化学。下一步，将制备含硼配位路易斯碱的金属硼烷衍生物。路易斯碱的引入将为合理改变金属硼烷的性质提供一种手段。最后，通过使用多面体环氧硼烷形成的硼-碳键将被开发为碳氢化合物功能化的途径。过渡金属的化学，当与含碳取代基结合时，是金属有机化学广阔领域的基础。这一领域的研究已经在理论化学和应用化学方面取得了许多进展。该项目旨在开辟一个过渡金属与含硼单元结合的相关领域。初步结果表明，这些“金属硼烷”将拥有广泛的化学，在某些方面类似于有机金属化学，但在其他方面却非常不同。在这项研究中，将制备新的硼烷和过渡金属的组合，并对它们的化学进行研究。这些新化合物将在新的反应化学中展示其电子结构的独特方面。除了科学贡献外，这个项目还将教授本科生、研究生和博士后同事尖端的合成无机化学，并将在口头和书面研究报告中为他们提供学习机会。该项目将包括女性科学家，包括来自不太注重研究的机构的教师。

Dr. Thomas P. Fehlner, Department of Chemistry, University of Notre Dame, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for the synthesis of new clusters containing both main-group and transition-metal atoms. The project has several areas of focus. The first involves an experimental and theoretical evaluation of the electronic structure of hypoelectronic metallaboranes, a set of metallaboranes of groups 6, 7 and 8 metals that exhibit highly condensed structures that differ qualitatively from other polyhedral borane and metal clusters and do not follow Wade's Rules. Secondly, metallaboranes will be used to modify organic substrates in which the characteristic reactivities of B-H and M-H fragments operate sequentially on a single bound organic substrate to generate novel hydrometallation chemistry. Next, metallaborane derivatives that contain boron-coordinated Lewis bases will be prepared. The incorporation of the Lewis bases will provide a means for rationally varying the properties of the metallaborane. Finally, boron-carbon bond formation through the use of polyhedral iridaboranes will be developed as a route to the functionalization of hydrocarbons. The chemistry of the transition metals, when combined with carbon-containing substituents, is the basis of the vast field of organometallic chemistry. Research in this area has led to many advances in pure and applied chemistry. This project aims to open a related area in which transition metals are combined with units containing boron. Preliminary results indicate that these "metallaboranes" will possess an extensive chemistry that in some ways resembles organometallic chemistry, but in other ways is very different. In this investigation new combinations of boranes and transition metals will be prepared and their chemistry investigated. The new compounds will express the unique aspects of their electronic structures in new kinds of reaction chemistry. In addition to the scientific contributions this project will teach undergraduate, graduate and postdoctoral coworkers cutting-edge synthetic inorganic chemistry and will provide them with learning opportunities in oral and written research presentation. The project will involve women scientists, including faculty from less research-oriented institutions.