Dithiolate Complexes of Manganese and Rhenium: X-ray Structure and Properties of an Unusual Mixed Valence Cluster Mn<sub>3</sub>(CO)<sub>6</sub>(μ-η<sup>2</sup>-SCH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>S)<sub>3</sub>
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Treatment of Mn2(CO)10 with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me3NO·2H2O in CH2Cl2 at room temperature afforded the dinuclear complexes Mn2(CO)6(μ-η4-SC6H3(CH3)S−SC6H3(CH3)S) (1), and Mn2(CO)6(μ-η4-SCH2CH2S−SCH2CH2S) (2), respectively. Similar reactions of Re2(CO)10 with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re2(CO)6(μ-η4-SC6H3(CH3)S−SC6H3(CH3)S) (3), Re2(CO)6(μ-η4-SC6H4S−SC6H4S) (4), and Re2(CO)6(SCH2CH2S−SCH2CH2S) (5), respectively. In contrast, treatment of Mn2(CO)10 with 1,3-propanedithiol afforded the trimanganese compound Mn3(CO)6(μ-η2-SCH2CH2CH2S)3 (6), whereas Re2(CO)10 gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1−5 contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn2(CO)6(μ-η4-SC6H4S−SC6H4S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV−vis and EPR spectroscopies as well as electrochemical techniques.
