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

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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.