Metallaborane Chemistry: From Small Heterobimetallaboranes to Large Metallaheteroboranes

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Dr. Lawrence Barton, Chemistry Department, University of Missouri-St. Louis, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for research on metallaborane chemistry. Heterobimetallaboranes that are derived from polyhedral boranes by substituting two of the boron vertices by various metals will be synthesized. Early transition metals will be combined with late metals to obtain species with metals of different electronic configurations. Since early transition metal complexes are good polymerization catalysts, heterobimetallaboranes containing only these metals will be prepared and evaluated as borane oligomerization catalysts. The work will be extended to the incorporation of main group nonmetal atoms into a monometallaborane. Routes to large cage derivatives will be sought and the mechanisms of cluster substitution processes will be evaluated. Boranes form a series of compounds and ions with regular structures in which boron-hydrogen units define the vertices of polyhedra. The ability of boron to support these cage structures is unique. The object of this project is to substitute some of the vertices in such cages with non-boron atoms. Special emphasis will be placed on examples with two transition metals and ones with a transition metal and a main-group nonmetal atom. These species will be designed as possible catalysts and as probes to determine the details of how substitution occurs in the boranes. This latter objective is important to preparing new metallaboranes of specific shape and composition. In addition to the new chemistry that will be uncovered in this project, postdoctoral, graduate, and undergraduate students will be educated in the very precise experimental techniques required for the investigation of boron hydrides.