Unexpected products resulting from reactions of Cp [formula omitted] (Me 2T = 2,5-dimethylthiophene) with (μ-S) 2Fe 2(Co) 62− and (μ-CO)(α-RS)Fe 2(CO) 6−

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The reactions of Cp ∗ Ir(η 5-2,5- Me 2 T) 2+ ( 1) with (μ-S) 2Fe 2(CO) 6 2− and ( μ-CO)( μ- n-BuS)Fe 2(CO) 6 −, which are expected to result in either reduction of 1 or nucleophilic attack on the η 2-2,5-dimethylthiophene ring, yield products that contain the reduced Cp ∗ Ir(η 4-2,5- Me 2 T) ( 2) ligand. X-ray diffraction studies of the producs Cp ∗ Ir(η 4-2,5- Me 2 T · Fe 2( CO) 5(μ- S 2) ) ( 6 and Cp ∗ Ir(α 4-2,5- Me 2 T · Fe 2( CO) 5(μ- S nBu ) 2) ) ( 9) show that the Cp ∗ Ir(α 4-2,5- Me 2 T) is coordinated through its sulfur atom to an Fe two bridging sulfur atoms of the Fe 2(μ-S) 2(CO) 4 core are bonded at two carbons of a rearrangement 2,5-Me 2T ligand. Characterization and mechanisms of formation of the new compounds are discussed.