Kinetic, mechanistic and spectral investigations of ruthenium(III)-catalysed oxidation of 4-hydroxycoumarin by alkaline diperiodatonickelate(IV) (stopped flow technique)

Shettar, R. S.; Nandibewoor, Sharanappa T.

doi:10.1016/j.molcata.2005.02.026

Cited by 38 publications

(26 citation statements)

References 21 publications

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“…Transition metals in a higher oxidation state can be stabilized by chelation with suitable polydentate ligands. Metal chelates such as diperiodatocuprate(III) (DPC), diperiodatoargentate(III) and diperiodatonickellate(IV) are good oxidants in a medium with suitable pH value. Copper(III) is an intermediate product formed in the copper(II)‐catalysed oxidation of amino acids by peroxydisulfate.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium(III) catalysed and uncatalysed oxidative mechanisms of methylxanthine drug theophylline by copper(III) periodate complex in alkali media: a comparative approach

Magdum

Bagoji

Nandibewoor

2015

J of Physical Organic Chem

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The kinetics of oxidation of methylxanthine drug, theophylline (TP), by diperiodatocuprate(III) (DPC) has been investigated in the absence and presence of ruthenium(III) (Ru(III)) as homogeneous catalyst in alkaline medium at a constant ionic strength of 0.21 mol dm−3 spectrophotometrically. The reaction exhibits 1:4 stoichiometry ([TP] : [DPC]) in both the cases. The order of the reaction with respect to [DPC] was unity, while the order with respect to [TP] was less than unity over the concentration range studied in both the cases. The rate was increased with an increase in [OH−] and decreased with an increase in [IO4−]. The order with respect to [Ru(III)] was unity. The ionic strength and dielectic constant of the medium did not affect the rate significantly. The main product 1‐methyl‐(3‐N‐formyl)‐2,4‐purinodione was identified by spot tests, Fourier transform infrared spectroscopy and liquid chromatography–mass spectrometry spectral studies. Based on the experimental results, the possible mechanisms were proposed. The reaction constants involved in the different steps of the mechanisms were evaluated. The catalytic constant (Kc) was also calculated for Ru(III) catalysis at different temperatures. The activation parameters with respect to the catalyst and slow step of the mechanisms were computed, and thermodynamic quantities were determined. Kinetic studies suggest that the active species of DPC and Ru(III) are found to be [Cu(H2IO6)(H2O)2] and [Ru(H2O)5OH]2+, respectively. Copyright © 2015 John Wiley & Sons, Ltd.

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Section: Introductionmentioning

confidence: 99%

Ruthenium(III) catalysed and uncatalysed oxidative mechanisms of methylxanthine drug theophylline by copper(III) periodate complex in alkali media: a comparative approach

Magdum

Bagoji

Nandibewoor

2015

J of Physical Organic Chem

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“…Transition metals in their higher oxidation states can generally be stabilized by chelation with suitable polydentate ligands. Metal chelates such as diperiodatocuprate(III) [7], diperiodatoargentate(III) [8] and diperiodatonickelate(IV) [9] are good oxidants in a medium with an appropriate pH value. Diperiodatocuprate(III) is a versatile one-electron oxidant and the oxidation study of DPC is scanty in view of its limited solubility and stability in aqueous medium.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of a Anticholinergic Drug Atropine Sulfate Monohydrate by Alkaline Copper(III) Periodate Complex: A Kinetic and Mechanistic Study

Byadagi

Hosahalli

Nandibewoor

et al. 2012

Zeitschrift Für Physikalische Chemie

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The oxidation of a anticholinergic drug, Atropine sulfate monohydrate (ASM) by diperiodatocuprate(III) (DPC) has been investigated spectrophotometrically in aqueous alkaline medium at a constant ionic strength of 0.50 mol dm-3. The reaction between diperiodatocuprate(III) and atropine sulfate exhibits 1:2 stoichiometry (atropine sulfate: diperiodatocuprate(III)). The main oxidation products were identified and confirmed by spectral studies including IR, 1H NMR and GC-MS. A suitable mechanism is proposed. The order with respect to diperiodatocuprate(III) concentration was unity, while the order with respect to atropine sulfate concentration was less than unity over the concentration range studied. The rates increased with an increase in alkali concentration and decreased with an increase in periodate concentration. The activation parameters with respect to slow step of the mechanism were calculated and the thermodynamic quantities we are also determined. Kinetic experiments suggest that [Cu(OH)2(H3IO6)] - is the reactive species of copper(III).

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“…In recent years, the kinetics and mechanism of oxidation of several organic compounds by silver (III) [23][24][25] cuprate (III) [26][27][28] and nickelate (IV) [29,30] complexes have been extensively studied. We have reported some investigations concerning CL reaction between luminol-H 2 O 2 enhanced by cuprate (III) [15,31]; the use of DPA and DPN in CL analysis has never been studied.…”

Section: Introductionmentioning

confidence: 99%

Flow injection determination of hydrogen peroxide using diperiodatoargentate- and diperiodatonickelate-luminol chemiluminescence

Yang

Zhang

2012

International Journal of Environmental Analytical Chemistry

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Kinetic, mechanistic and spectral investigations of ruthenium(III)-catalysed oxidation of 4-hydroxycoumarin by alkaline diperiodatonickelate(IV) (stopped flow technique)

Cited by 38 publications

References 21 publications

Ruthenium(III) catalysed and uncatalysed oxidative mechanisms of methylxanthine drug theophylline by copper(III) periodate complex in alkali media: a comparative approach

Ruthenium(III) catalysed and uncatalysed oxidative mechanisms of methylxanthine drug theophylline by copper(III) periodate complex in alkali media: a comparative approach

Oxidation of a Anticholinergic Drug Atropine Sulfate Monohydrate by Alkaline Copper(III) Periodate Complex: A Kinetic and Mechanistic Study

Flow injection determination of hydrogen peroxide using diperiodatoargentate- and diperiodatonickelate-luminol chemiluminescence

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