103383-36-4Relevant academic research and scientific papers
Oxidation at a Dimolybdenum(V) Sulfur Bridge. Formation of so and SO2 Bridges. Facile Extrusion of so from the SO2 Bridge
Wang, Runtong,Mashuta, Mark S.,Richardson, John F.,Noble, Mark E.
, p. 3022 - 3030 (2008/10/09)
Peroxide oxygenation of μ-thiolate-μ-sulfide Mo(V) dimer complexes of the type [Mo2(NAr)2(S2P(OEt)2) 2(μO2CMe)(μ-SR)(μ-S)] yielded Mo2(μ-SO) and Mo2(μ-SO2) complexes, demonstrating the reactivity sequence μ-S > μ-SO ? μ-SR. Inversion isomers of the pyramidal sulfur site in the μ-SO bridge were observed, and the pyramidicity was confirmed crystallographically. Visible light photolysis of the Mo2(μ-SO2) complex liberated SO from the SO2 bridge and produced Mo2(μ-O) compounds. Crystallography of analogous Mo2(μ-S), Mo2(μ-SO), Mo2(μ-SO2), and Mo2(μ-O) complexes provided structural comparisons related to variations in the bridge functionality. For 2, Mo2C31H44N2O6P 2S6: a = 13.604(5) A?, b = 15.280(4) A?, c = 12.502(2) A?, α = 93.36(2)°, β = 112.00 (2)°, γ = 76.01(2)°, triclinic, P1, Z = 2. For 3, Mo2C31H44N2O7P 2S6: a = 12.535(2) A?, b = 25.299-(9) A?, c = 13.989(5) A?, β = 99.99(2)°, monoclinic, P21/n, Z = 4. For 4, Mo2C31H44N2O8P 2S6: a = 12.591(9) A?, b = 25.34(1) A?, c = 14.048(3) A?, β = 100.79(4)°, monoclinic, P21/n, Z = 4. For 5, Mo2C31H44N2O7P 2S5: a = 13.731(5) A?, b = 19.267(4) A?, c = 16.652(5) A?, β = 104.78(3)°, monoclinic, P21/n, Z = 4.
Reactions at a dimolybdenum(V) sulfur bridge. Formation of disulfide (S22-), monosubstituted organic disulfide (RSS-), and tetrasulfide (S42-) bridges
Noble, Mark E.
, p. 3311 - 3317 (2008/10/08)
Compounds of the general form [Mo2(NAr)2(S2P(OC2H 5)2)2S(O2CR)]2(S 2) (Ar = C6H5, p-C6H4CH3; R = alkyl, aryl) were prepared by the reaction of [Mo(NAr)(S2P(OC2H5)2)S]4 with H2O2 in the presence of a carboxylic acid. The compounds contain a disulfide linkage bridging in inter- and intradimer fashion, formed by the oxidation of two Mo2S26+ cores to give SMo2SSMo2S, formally equivalent to SMo2S? thiyl radical coupling. Mixed dimer-organic disulfides were prepared by the reaction of [Mo2-(NC6H4CH3)2(S 2P(OC2H5)2)2S 2(O2CCH3)]- with sulfenyl chlorides, R′SCl (R′ = alkyl, aryl). The products, [Mo2-(NC6H4CH3)2(S 2P(OC2H5)2)2S(O 2CCH3)(SSR′)], contain an unusual R′SS- linkage to the two Mo(V) sites within the dimer, representable by SMo2SSR′, wherein the monosubstituted organic disulfide ion bridges by its β-sulfur. A bridge tetrasulfide, [Mo2(NC6H4CH3)2(S 2P(OC2H5)2)2S(O 2CCH3)]2(S4), was prepared by the reaction of [Mo2(NC6H4CH3)2(S 2P(OC2H5)2)2S 2-(O2CCH3)]- with S2Cl2 and contains the SMo2SSSSMo2S unit, in which the tetrasulfide bridges also in inter- and intradimer fashion via its terminal sulfur atoms. Most of the compounds show stereoisomers related by bridge sulfur inversion. Reactions with triphenylphosphine gave either desulfurization or reduction.
