Halogenation At A Dimolybdenum(V) And Ditungsten(V) Sulfur Bridge - Metallosulfenyl Halides M(2)(Mu-Sx) And [M(2)(Mu-Sx(3))](N) - Charge-Transfer Interactions

The reactions of halogens at anionic, radical, and neutral bridge sulfur sites within M(2)S(2) cores of various [M(2)-(NAr)(2)(S2P(OEt)(2))(2)(mu-S)(2)(mu-O(2)CMe)] compounds (M = Mo, W) produced covalent halosulfide ligands. Complexes containing the W-2(mu-SX) unit were obtained for X = Cl, Br, and I; trihalide polymers of [M(2)(mu-SX(3))](n) units were obtained for M = W or Mo and X = Br or I. These latter compounds engaged in depolymerization equilibria in solution. The derivative containing the structural unit [Mo-2(mu-SI3)](n) undergoes photolysis in fluorescent light to I-2 and a disulfide of the type Mo2S-SMo2. Crystallography of the W-2(mu-SBr) product clearly revealed the discrete bromosulfide bridge ligand, mu-SBr. Crystallography of the [Mo-2(mu-SI3)](n) product revealed SX(3)S(3-) ligands which interconnected the Mo-2 structural units into one-dimensional polymer chains. Simple charge transfer interactions between metallosulfur sites of various derivatives and iodine were also observed.