Carbon-Sulfur and Carbon-Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo2Cp2(μ-SMe)3(MeCN)2]

Reactions of the trithiolato-bridged complex [Mo2Cp2(mu-SMe)3(MeCN)(2)](BF4) (1) with acyclic (e.g., Et2S) or cyclic (e.g., thiirane, thietane, tetrahydrothiophene, 1,4-dithiane, and 1,4-thioxane) thioethers and chalcogenophenes (benzothiophene, benzoselenophene, and dibenzothiophene) in dihaloalkanes led to either the thioether- and halide-bridged compounds [Mo2Cp2(mu-SMe)2(mu-SRR')(mu-X)](BF4) (R = R' = Et, X = Cl (3); RR' = C4H8, X = Cl (10), X = Br (11); RR' = C4H8O, X = Cl (14)), and dithioether- and chloro-bridged derivatives [Mo2Cp2(mu-SMe)(2)(mu-Cl){mu-kappa(1) (S), k(1)(S)-(SR ''(x)(CH2)(n)SR ''(x)}](BF4) (x = 1, R '' = Me, n = 1 (4); x = 0, n = 4 (13)) or the mu-sulfido complex [MO2Cp2(mu-SMe)(3)(mu-S)](BF4) (6) and the methyl 1,3-propylthiolate thioether-bridged compound [MO2Cp2(mu-SMe)(2){mu-k(2)(S),k(2)-S(CH2)(3)SMe}](BF4) (8), according to the structural features of the organic sulfur reagents. Ring-opening reaction through the cleavage of C-S bonds occurred when small-ring thiethers (e.g., thiirane and thietane) are used as reagents, whereas facile C-X (X = Cl, Br) bond cleavage was observed for other sulfur molecules. Some reactions that were conducted in chlorocarbon solvents (e.g., CH2Cl2, (CH2)(2)Cl-2) gave rise to the formation of the oxo-bridged complex [Mo(2)CP2(mu-SMe)(3)(mu-O)](BF4) (7) as a byproduct with moderate yields. All new complexes have been characterized by elemental analyses and spectroscopic methods, supplemented for the tetraphertylborate or hexafluorophosphate salts of 4, 6-8, 10, and 13 by X-ray diffraction.