Carborane-Stabilized Mixed-Valence Metallooligomers

无机化学、生物无机化学和金属有机化学项目的这一奖项支持弗吉尼亚大学化学系的Russell N.Grimes对混合价金属碳硼烷的研究。我们将合成一些双核和多核过渡金属碳硼烷。这些是可溶的顺磁性络合物，具有两个或更多过渡金属-碳硼烷单元，通过共价键连接，旨在允许分子内金属-金属通信。小碳硼烷配体将被用来稳定络合物，允许以稳定的、可溶的形式直接合成一系列分子结构。主要目的是探索金属-金属通讯对结构几何、金属和金属氧化态的选择、连接基的数量和性质以及连接基与金属碳硼簇合物单元的结合方式的依赖。要研究的结构是末端带有金属的链、内部金属化的线性系统和支链化合物。连接物将包括炔基、烯基和苯基单元。这些化合物将通过各种方法进行表征，包括X射线衍射、EPR、核磁共振和循环伏安。将开发新的合成方法来获得具有特定结构设计的化合物。获得的这些化合物将用于探索含有混合氧化态金属的系统中金属之间的相互作用。这一结果将与具有特定电、磁或光学特性的材料的设计相关。研究生将接受各种先进方法和具有挑战性的合成工作的培训。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research by Russell N. Grimes, Chemistry Department, University of Virginia, on mixed-valence metallo-carboranes. Selected families of dinuclear and polynuclear transition metal metallacarboranes will be synthesized. These are soluble paramagnetic complexes featuring two or more transition metal-carborane units connected by covalently bonded linkers designed to permit intramolecular metal-metal communication. Small carborane ligands will be used to stabilize the complexes, permitting directed synthesis of a range of molecular architectures in stable, soluble form. The primary goal is to explore the dependence of metal-metal communication on structural geometry, choice of metals and metal oxidation states, the number and nature of the linkers, and the mode of binding of the linking groups to the metallacarborane cluster units. The architectures to be investigated are chains with metals at the ends, internally metallated linear systems, and branched chain compounds. The connectors will include alkynyl, alkenyl, and phenylene units. The compounds will be characterized by a variety of methods, including X-ray diffraction, EPR, NMR, and cyclic voltammetry.New synthetic methods will be developed to obtain compounds with specific architectural designs. These compounds obtained will be used to explore interaction between metals in systems that contain metals that have a mixture of oxidation states. The results will be relevant to design of materials with specified electronic, magnetic, or optical properties. Graduate students will receive training in a variety of advanced methods and challenging synthetic work.