Disulfides of Manganese Carbonyl. Synthesis of Mn2(CO)7(μ-S2) and Its Reactions with Tertiary Phosphines and Arsines

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posted on 2002-11-02, 00:00 authored by Richard D. Adams, O-Sung Kwon, Mark D. Smith

The reaction of Mn2(CO)9(NCMe) with thiirane yielded the sulfidomanganese carbonyl compounds Mn2(CO)7(μ-S2), 2, Mn4(CO)15(μ3-S2)(μ4-S2), 3, and Mn4(CO)14(NCMe)(μ3-S2)(μ4-S2), 4, by transfer of sulfur from the thiirane to the manganese complex. Compound 3 was obtained in better yield from the reaction of 2 with CO, and compound 4 is obtained from the reaction of 2 with NCMe. The reaction of 2 with PMe2Ph yielded the tetramanganese disulfide Mn4(CO)15(PMe2Ph)2(μ3-S)2, 5, and SPMe2Ph. The reaction of 5 with PMe2Ph yielded Mn4(CO)14(PMe2Ph)3(μ3-S)2, 6, by ligand substitution. The reaction of 2 with AsMe2Ph yielded the new complexes Mn4(CO)14(AsMe2Ph)2(μ3-S2)2, 7, Mn4(CO)14(AsMe2Ph)(μ3-S2)(μ4-S2), 8, Mn6(CO)20(AsMe2Ph)2(μ4-S2)3, 9, and Mn2(CO)6(AsMe2Ph)(μ-S2), 10. Reaction of 2 with AsPh3 yielded the monosubstitution derivative Mn2(CO)6(AsPh3)(μ-S2), 11. Reaction of 7 with PMe2Ph yielded Mn4(CO)15(AsMe2Ph)2(μ3-S)2, 12. The phosphine analogue of 7, Mn4(CO)14(PMe2Ph)2(μ3-S2)2, 13, was prepared from the reaction of Mn2(CO)9(PMe2Ph) with Me3NO and thiirane. Compounds 2−9 and 11−13 were characterized by single-crystal X-ray diffraction. Compound 2 contains a disulfido ligand that bridges two Mn(CO)3 groups that are joined by a Mn−Mn single bond, 2.6745(5) Å in length. A carbonyl ligand bridges the Mn−Mn bond. Compounds 3 and 4 contain four manganese atoms with one triply bridging and one quadruply bridging disulfido ligand. Compounds 5 and 6 contain four manganese atoms with two triply bridging sulfido ligands. Compound 9 contains three quadruply bridging disulfido ligands imbedded in a cluster of six manganese atoms.