Metallacarboranes of Main Group, Transition, and Lanthanide Elements: Syntheses, Structures and Reactivities

化学系的无机，生物无机和有机化学计划支持Narayan S。Hosmane，北方伊利诺伊大学化学和生物化学系，研究主族、过渡族和镧系元素的金属碳硼烷的合成、结构和反应性。 该项目有三个主要目标。第一个是从容易制备和/或可获得的硼烷试剂（例如Na（B3 H8））开发天然和10 B-富集的C2 B4-碳硼烷的方便、安全的合成。目标是一种不需要真空管线的制备路线，从而使在硼烷和碳硼烷操作方面没有经验的实验室能够利用这些化合物。其次，将使用活性金属介导的还原性开笼反应制备各种离子和中性金属碳硼烷，其含有跨越第2-14族的金属，伴随着打开的碳硼烷表面的金属化。具体目的是获得一系列化合物-从水溶性metallacarborane盐到亲脂性中性metallacarborane-的受限几何半和全夹心有机金属物种。最后，阳离子亲电金属碳硼烷将用C2 B4-和C2B 9-或C2 B10-碳硼烷制备，C2 B4-和C2B 9-或C2 B10-碳硼烷都与金属配位并充当弱配位阴离子。这些将作为烯烃聚合的催化剂进行研究。本研究的目标是生产一些新的和新颖的化合物，其含有碳和/或硼结合多种金属的笼。虽然含有碳和硼的笼状化合物已经知道了一段时间，但它们需要非常复杂的技术来方便和安全地制备它们。因此，该项目的第一部分将是设计新的制备程序，使这些物种能够在典型的实验室中合成。下一节将开发在正常环境条件下稳定的各种硼碳笼分子的路线。高水溶性和脂溶性的物种可能是有用的应用，如硼中子捕获治疗和均相催化。参与这个项目的学生，无论是研究生还是本科生，都将学习广泛的综合技能。此外，他们还将与几个国家实验室、其他大学和研究机构以及BP/Amoco的一些合作者一起参与。因此，他们将参加一个真正的跨学科研究项目，在科学和工程的接口。

The Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division supports Dr. Narayan S. Hosmane, Department of Chemistry and Biochemistry Northern Illinois University, for research into the synthesis, structure, and reactivity of metallacarboranes of main-group, transition, and lanthanide elements. The project has three main thrusts. The first is the development of a convenient, safe synthesis of natural and 10B-enriched C2B4-carboranes from readily prepared and/or available borane reagents, such as the Na(B3H8). The objective is a preparative route that does not require a vacuum line, thus enabling laboratories not experienced in the manipulation of boranes and carboranes to utilize these compounds. Secondly, a variety of ionic and neutral metallacarboranes, containing metals spanning groups 2-14, will be prepared using active-metal mediated reductive cage-opening reactions, with concomitant metalation of the opened carborane face. The specific purpose is to obtain a range of compounds- from water-soluble metallacarborane salts to lipophilic neutral metallacarboranes-of both the constrained geometry half- and full-sandwich organometallic species. Finally, cationic electrophilic metallacarboranes will be prepared with C2B4- and C2B9- or C2B10- carboranes both coordinating to the metal and serving as weakly coordinating anions. These will be studied as catalysts for olefin polymerization. The goal of this research is to produce a number of new and novel compounds containing cages of carbon and/or boron combined a wide range of metals. While cage compounds containing carbon and boron have been known for some time, they require very sophisticated techniques in order to prepare them conveniently and safely. Thus, the first part this project will be the design new preparative procedures that will allow these species to be synthesized in typical laboratories. The next section will develop routes to a variety of boron-carbon cage molecules that are stable under normal environmental conditions. The highly water- and fat-soluble species might be useful in applications such as Boron Neutron Capture Therapy and in homogeneous catalysis. The students involved in this project, both graduates and undergraduates, will learn a breadth of synthetic skills. Additionally, they will be involved with a number of collaborators at several national laboratories, other universities and research institutions, and at BP/Amoco. Thus they will take part in a true interdisciplinary research project at the interface of science and engineering.