The influence of the nature of bridging carboxylates on the structure and reactivity of diruthenium(I,I) core complexes has been studied. A family of mixed-ligand complexes, [Ru2(O2CR)2(CO)5]2 (R = CF3, C6F5, C6H3(CF3)2), has been prepared and structurally characterized. A ¢dimer of dimers¢ type of structure in which dimetal units are bound in the solid state through axial Ru…O interactions or direct Ru…Ru contacts has been revealed. Reactivity tests toward various donor substrates have confirmed the formation of dimetal core units in gas-phase and in solution reactions. The dinuclear complexes show electrophilic properties at open ruthenium(I) ends enhanced by the presence of bridging fluorinated carboxylates. Such properties are related to the catalytic activity of the diruthenium(I,I) complexes found in O—H insertion reactions of vinylcarbenoids. The [Ru2(O2CCF3)2(CO)5]2 catalyst showed a better performance in the vinyl terminus reactions possibly due to the greater electronic deficient character at the rurhenium(I) centers.
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