Systematic Metallaborane Reaction Chemistry

圣母大学化学系的托马斯·P·费尔纳博士得到化学系无机、生物无机和有机物计划的支持，用于合成含有主族和过渡金属原子的新簇。该项目有几个重点领域。第一个涉及亚电子金属硼烷的电子结构的实验和理论评估，一组金属硼烷的第6，7和8族金属，表现出高度凝聚的结构，从定性上不同于其他多面体硼烷和金属簇，不遵循韦德规则。其次，金属硼烷将用于修饰有机底物，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依次起作用，以产生新的氢金属化化学。接着，制备含有硼配位的刘易斯碱的金属硼烷衍生物。引入刘易斯碱将提供合理改变金属硼烷性质的方法。最后，硼-碳键的形成，通过使用多面体iridaboranes将开发作为一种途径的烃的官能化。过渡金属的化学，当与含碳取代基结合时，是有机金属化学的广阔领域的基础。这一领域的研究导致了纯化学和应用化学的许多进展。该项目旨在开辟一个过渡金属与含硼单元相结合的相关领域。初步结果表明，这些“金属硼烷”将拥有广泛的化学性质，在某些方面类似于有机金属化学，但在其他方面非常不同。在这项调查中，新的组合硼烷和过渡金属将制备和他们的化学研究。新化合物将在新的反应化学中表达其电子结构的独特方面。除了科学贡献外，该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，并为他们提供口头和书面研究报告的学习机会。该项目将涉及女科学家，包括来自研究较少的机构的教员。

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.