title: The reduction of CrVI to CrIII by the alpha and beta anomers of D-glucose in dimethyl sulfoxide. A comparative kinetic and mechanistic study.
abstract: The reduction of CrVI by alpha-D-glucose and beta-D-glucose was studied in dimethyl sulfoxide in the presence of pyridinium p-toluensulfonate, a medium where mutarotation is slower than the redox reaction. The two anomers reduce CrVI by formation of an intermediate CrVI ester precursor of the slow redox step. The equilibrium constant for the formation of the intermediate chromic ester and the rate of the redox steps are different for each anomer. alpha-D-Glucose forms the CrVI-Glc ester with a higher equilibrium constant than beta-D-glucose, but the electron transfer within this complex is slower than for the beta anomer. The difference is attributed to the better chelating ability of the 1,2-cis-diolate moiety of the alpha anomer. The CrV species, generated in the reaction mixture, reacts with the two anomers at a rate comparable with that of CrVI. The EPR spectra show that the alpha anomer forms several linkage isomers of the five-coordinate CrV bis-chelate, while beta-D-glucose affords a mixture of six-coordinate CrV monochelate and five-coordinate CrV bis-chelate. The conversion of the CrV mono- to bis-chelate is discussed in terms of the ability of the 1,2-cis- versus 1,2-trans-diolate moieties of the glucose anomers to bind CrV.
authors.affiliation: Departamento de Química, Facultad de Ciencias Bioquímicas y Farmacéuticas, UNR, Rosario, Argentina.
authors.forename: S
authors.initials: S
authors.lastname: Signorella
authors.forename: R
authors.initials: R
authors.lastname: Lafarga
authors.forename: V
authors.initials: V
authors.lastname: Daier
authors.forename: L F
authors.initials: LF
authors.lastname: Sala
mesh_terms: D001557:Benzenesulfonates; D002614:Chelating Agents; D017608:Chromium Compounds / Q000737:chemistry*; D004121:Dimethyl Sulfoxide; D005942:Gluconates / Q000138:chemical synthesis; D005947:Glucose / Q000737:chemistry*; D007700:Kinetics; D008968:Molecular Conformation; D009904:Optical Rotation; D010084:Oxidation-Reduction; D011726:Pyridinium Compounds; D012997:Solvents; D013237:Stereoisomerism
chemical_list: D001557:Benzenesulfonates; D002614:Chelating Agents; D017608:Chromium Compounds; D005942:Gluconates; D011726:Pyridinium Compounds; D012997:Solvents; D005947:Glucose; C029501:4-toluenesulfonic acid; C030691:gluconic acid; D004121:Dimethyl Sulfoxide