Preparation, Studies, and Applications of Lanthanide-Transition Metal Arrays: Cyclic Organohydroborate Derivatives of Lanthanides and Metallocenes

谢尔顿G博士。海岸，俄亥俄州州立大学化学系，由化学系的无机，生物无机和有机化学计划支持，用于研究镧系元素-过渡金属阵列和含有环状有机硼氢化物部分的镧系元素和茂金属络合物。该项目有两个主要目标。第一是制备和研究由镧系元素和过渡金属的组合组成的配合物。将制备含有阴离子三维阵列（CuCN）的络合物，镧系元素被螯合到所述阴离子三维阵列中。另外，目标是在过渡金属如Co和镧系金属如Yb之间含有羰基桥的三维扩展阵列和由连接到过渡金属羰基化物阴离子的镧系金属如Yb的羟基-氧代-簇组成的三维阵列。这些物质将作为各种工艺的催化剂进行评价。该项目的第二个方面涉及制备和研究含有环状有机硼氢化物[H2 BC 8H 14]阴离子的镧系元素和三烯的环状有机硼氢化物衍生物。镧系元素硼氢化物近年来受到了零星的关注，对镧系元素（II）氧化态的氢溴酸盐衍生物的研究非常有限。初步结果表明，不寻常的agostic在这些物种的相互作用和他们的能力进行氢化物提取的Ln-H-B桥将进行评估。 含有过渡金属的无机配合物显示出许多有趣和有用的性质。许多这样的化合物具有催化工业过程和新有机化合物（包括药物）合成中使用的重要化学转化的能力。含有过渡金属原子和镧系元素（“稀土元素”，如镱或钆）原子的化合物迄今为止是罕见的。有充分的理由期待这些化合物将具有新颖，有趣和重要的特性，例如催化重要化学反应的能力。在过去NSF支持的成功研究中获得的经验的基础上，海岸和他的同事们将设计方法来制备含有镧系元素和过渡金属原子的化合物，表征这些化合物，并探索它们的性质。此外，还将制备含有两个互连硼原子的基团的新型化合物，并探索其性质。 参与这项工作的研究生将获得金属和主族化学以及相关工程领域的几个方面的专业知识。

Dr. Sheldon G. Shore, Chemistry Department, Ohio State University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for research into lanthanide-transition metal arrays and into lanthanide and metallocene complexes that contain cyclic organohydroborate moieties. The project has two main objectives. The first is to prepare and study complexes that are composed of combinations of lanthanide and transition metals. Complexes containing an anionic three dimensional array (CuCN) into which a lanthanide element is sequestered will be prepared. Additionally, three dimensional extended arrays that contain carbonyl bridges between a transition metal such as Co and a lanthanide metal such as Yb and three dimensional arrays that are composed of hydroxo-oxo-clusters of a lanthanide such as Yb linked to transition metal carbonylate anions will be targeted. These species will be evaluated as catalysts for a variety of processes. The second aspect of the project involves the preparation and study of cyclic organohydroborate derivatives of lanthanides and metallocenes which incorporate the cyclic organohydroborate [H2BC8H14] anion. Lanthanide hydroborates have received sporadic attention over the years and investigations of hydrobroate derivatives of lanthanides in the (II) oxidation state have been extremely limited. Preliminary results indicate unusual agostic interactions in these species and their ability to undergo hydride abstraction from the Ln-H-B bridge will be evaluated. Inorganic complexes that contain transition metals display a great variety of interesting and useful properties. Many such compounds have the ability to catalyze important chemical transformations used in industrial processes and in the synthesis of new organic compounds, including pharmaceuticals. Compounds that contain both transition metal atoms and also lanthanide ("rare earth elements" such as ytterbium or gadolinium) atoms have heretofore been rare. There are good reasons to expect that such compounds will have novel, interesting and important properties, such as the ability to catalyze important chemical reactions. Building on experiences gained in successful research supported by NSF in the past, Shore and his colleagues will devise methods to prepare compounds containing both lanthanide and transition-metal atoms, characterize those compounds, and explore their properties. In addition, new types of compounds containing groups of two interlinked boron atoms will also be prepared and their properties explored. Graduate students involved in this work will acquire expertise in several aspects of metal and main group chemistry, as well as in related areas of engineering.