Reactions of Thioethers with Mn₂(CO)₇(μ-S₂) Proceed with CO Displacement and Insertion of the Sulfur Atom into the Mn−Mn Bond

The reaction of Mn2(CO)7(μ-S2) (2) with SMe2 yielded the new complexes Mn2(CO)6(μ-S2)(μ-SMe2) (3) and Mn4(CO)14(SMe2)(μ3-S2)(μ4-S2) (4) in 18 and 41% yields, respectively. The reaction of 2 with the cyclic thioether thietane SCH2CH2CH2 yielded the new complexes Mn2(CO)6(μ-S2)(μ-SCH2CH2CH2) (5) and Mn4(CO)14(SCH2CH2CH2)(μ3-S2)(μ4-S2) (6) in 12 and 52% yields, respectively, and the reaction of 2 with 1,4,9-trithiacyclododecane (12S3) yielded Mn2(CO)6(μ-12S3)(μ-S2) (7) and Mn4(CO)14(12S3)(μ3-S2)(μ4-S2) (8) in 8 and 24% yields, respectively. Compounds 3 and 5−7 were characterized crystallographically. Compounds 3, 5, and 7 have similar structures in which the thioether ligand has replaced the bridging carbonyl ligand of 2 and its sulfur atom has been inserted into the manganese−manganese bond. The two manganese atoms are not mutually bonded, and two Mn(CO)3 groups are held together through the bridging disulfido ligand and the bridging sulfur atom of the thioether ligand. Compound 6 contains a Mn4(μ3-S2)(μ4-S2) moiety without metal−metal bonds. On the basis of spectroscopic data, compounds 4 and 8 are believed to have similar structures.