title: Pd(II)-catalysed and Hg(II)-co-catalysed oxidation of D-glucose and D-fructose by N-bromoacetamide in the presence of perchloric acid: a kinetic and mechanistic study.
abstract: The kinetics of Pd(II)-catalysed and Hg(II)-co-catalysed oxidation of D-glucose (Glc) and D-fructose (Fru) by N-bromoacetamide (NBA) in the presence of perchloric acid using mercury(II) acetate as a scavenger for Br- ions have been studied. The results show first-order kinetics with respect to NBA at low concentrations, tending to zero order at high concentrations. First-order kinetics with respect to Pd(II) and inverse fractional order in Cl- ions throughout their variation have also been noted. The observed direct proportionality between the first-order rate constant (k1) and the reducing sugar concentration shows departure from the straight line only at very higher concentration of sugar. Addition of acetamide (NHA) decreases the first-order rate constant while the oxidation rate is not influenced by the change in the ionic strength (mu) of the medium. Variation of [Hg(OAc)2] shows a positive effect on the rate of reaction. The observed negative effect in H+ at lower concentrations tends to an insignificant effect at its higher concentrations. The first-order rate constant decreases with an increase in the dielectric constant of the medium. The various activation parameters have also been evaluated. The products of the reactions were identified as arabinonic acid and formic acid for both the hexoses. A plausible mechanism involving HOBr as the reactive oxidising species, Hg(II) as co-catalyst, and [PdCl3.S]-1 as the reactive Pd(II)-sugar complex in the rate-controlling step is proposed.
authors.affiliation: Department of Chemistry, University of Allahabad, Allahabad 211002, India. ashokeks@rediffmail.com
authors.forename: Ashok Kumar
authors.initials: AK
authors.lastname: Singh
authors.forename: Jaya
authors.initials: J
authors.lastname: Srivastava
authors.forename: Shahla
authors.initials: S
authors.lastname: Rahmani
authors.forename: Vineeta
authors.initials: V
authors.lastname: Singh
mesh_terms: D000081:Acetamides / Q000494:pharmacology*; D002384:Catalysis; D004563:Electrochemistry; D019277:Entropy; D005609:Free Radicals / Q000378:metabolism; D005632:Fructose / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry*; D007700:Kinetics; D008628:Mercury / Q000494:pharmacology*; D010084:Oxidation-Reduction; D010165:Palladium / Q000494:pharmacology*; D010472:Perchlorates / Q000494:pharmacology*
chemical_list: D000081:Acetamides; D005609:Free Radicals; D010472:Perchlorates; C016272:N-bromoacetamide; D005632:Fructose; D010165:Palladium; D008628:Mercury; D005947:Glucose