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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of ruthenium(III) catalysis in the oxidation of erythritol and dulcitol byN-bromoacetamide (1991)
    Springer
    Transition metal chemistry 16 (1991), S. 610-613 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The kinetics of RuIII catalysed oxidation of erythritol (1,2,3,4-tetrahydroxybutane) and dulcitol (1,2,3,4,5,6-hexahydroxyhexane) byN-bromoacetamide (NBA) in HClO4 in the presence of Hg(OAc)2 as a scavenger for Br− have been investigated. The reactions are zeroth order with respect to both alcohols, and first order at low concentration of NBA tending to zero order at high NBA concentrations. The oxidation rate is directly proportional to [RuIII] and a positive effect on the rate is observed for [H+] and [Cl−] whereas a negative effect is observed for acetamide and ionic strength. D2O and Hg(OAc)2 do not influence the oxidation rate; (H2OBr)+ is postulated as the oxidising species. A suitable mechanism consistent with the observed kinetic data is proposed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01024198
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  • 2
    Electronic Resource
    Electronic Resource
    Ru(III) catalysis in N-bromoacetamide oxidation of ethylene glycol and glycerol: A kinetic and mechanistic study (1988)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 501-511 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of oxidation of ethylene glycol and glycerol by acidic solution of N-bromoacetamide (NBA) in the presence of ruthenium (III) chloride as a homogeneous catalyst and mercuric acetate as scavenger in the temperature range of 30-50°C have been reported. The reactions follow identical kinetics, being zero-order in substrate and first-order in Ru(III). First order dependence of the reaction on NBA at its low concentrations tends to zero order in the higher concentration range. Positive effect of [H-] and [Cl-] has been observed. A negative effect of acetamide and ionic strength of the medium is observed while D2O and mercuric acetate show zero effect on the reaction velocity. Various activation parameters have been computed. The main product of the oxidation is corresponding acid. (H2OBr)+ has been postulated as the oxidizing species. A suitable mechanism in conformity with the kinetic data has been proposed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550200702
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    Paper (German National Licenses)
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