title: Copper(II)-catalyzed disulfide scission--stepwise aerobic oxidative cleavage to sulfinate and sulfonate and reductive anaerobic cleavage to thiols.
abstract: The Cu(II)-catalyzed oxidative and reductive cleavage of the disulfide bond of N-(2-(2-(2-picolinamido)phenyl)disulfanyl)phenyl)picolinamide, L, is reported for the first time. Aerobic oxidation with Cu(II) gives complete oxidation of S-S bond to sulfonates, whereas Ag(I) gives only partial oxidation up to sulfinates, in the absence of any other oxidizing agent, in tetrahydrofuran/water solution. The in situ generated sulfonate product forms a thermally stable, two-dimensional H-bonded polymeric complex with Cu(II) ions in two polymorphic forms. L in the presence of Cu(II), in an inert atmosphere, results in a reductive cleavage of the disulfide bond and an in situ formation of a new C-S bond. The latter forms a unique tetranuclear complex with Cu(II) employing deprotonated amide groups and bridging thiol and chloride atoms. The disulfide precursor and the products were characterized by X-ray crystallography and spectroscopic techniques.
authors: Department of Chemistry, Centre for Advanced Studies in Chemistry, Guru Nanak Dev University , Amritsar-143005, India.
authors: Isha
authors: I
authors: Lumb
authors: Maninder Singh
authors: MS
authors: Hundal
authors: Geeta
authors: G
authors: Hundal
mesh_terms: D000693:Anaerobiosis; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D004220:Disulfides / Q000737:chemistry*; D010084:Oxidation-Reduction; D013057:Spectrum Analysis; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis*
chemical_list: D004220:Disulfides; D013438:Sulfhydryl Compounds; D003300:Copper