1. Magnetic Studies and Room Temperature Carbon-Carbon Bond Cleavage in Ruthenium Carboxylate Clusters
Laura E. Pence, Department of Chemistry, University of Hartford
Although the acetate species of oxo-bridged basic triruthenium carboxylate system, [Ru3O(O2CR)6(L)3]n, has been well-studied, examples of other carboxylate ligands in this system are less common, owing to challenges with optimizing both reaction conditions and with separation of the product salt from similarly charged by-products. Well-known for their extensive electrochemistry involving up to five different charges on the cluster, the trinuclear ruthenium compounds possessing water in the axial positions of the metals also display proton-coupled electron transfer, in which the aqua ligands are deprotonated to hydroxide, thus becoming resistant to subsequent pyridine exchange. Our investigations have focused on establishing a general pathway for the synthesis and purification of oxo-bridged triruthenium carboxylate species with longer chain carboxylates such as the isobutyrate, n-butyrate, and trimethylacetate species. The products have been studied via cyclic voltammetry and 1-D and 2-D 1H NMR, which has revealed unusual signal relaxation due to the proximity of the paramagnetic metal core.