Complex formation reaction of the iron(<scp>iii</scp>) hydroxo dimer with periodate ion

Kerezsi, Ildikó; Lente, Gábor; Fábián, István

doi:10.1039/b313341a

Cited by 17 publications

(16 citation statements)

References 29 publications

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“…In aqueous solutions, periodate is transformed into the three forms in water including orthoperiodic acid [7] governed by the equilibria (3-4) for which the dissociation constants are already reported [17,18].…”

Section: Rate Lawmentioning

confidence: 99%

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Manganese(II) catalyzed periodate oxidation of p-toluidine: a kinetic and mechanistic study

Kaushik

Kumar

et al. 2010

Reac Kinet Mech Cat

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The kinetics of the periodate oxidation of p-toluidine (TOL) in acetonewater medium has been followed by monitoring the increase in the absorbance of the reaction intermediate, C 4 , and the main reaction product is 4-methyl-1,2-benzoquinone. Results under pseudo first order conditions, substrate [S] and [IO 4-] 0 represents the concentration of periodate that has been taken in excess in most of the kinetic runs. In agreement with the rate law, the 1/k cat versus pH profile passes through a minimum. Free radical scavengers do not affect the reaction rate. The rate is found to decrease with an increase in ionic strength and decrease in dielectric constant of the medium. Activation parameters evaluated are: DE = 12.2 ± 1.1 kJ mol -1 , A = (1.57 ± 0.005) 9 10 7 dm 3 mol -1 s -1 ; DS # = -115.9 ± 0.2 J mol -1 K -1 , DG # = 46.2 ± 0.9 kJ mol -1 and DH # = 9.60 ± 0.06 kJ mol -1 .

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Section: Rate Lawmentioning

confidence: 99%

“…Some of the recent reports include the Mn(II) catalyzed oxidation of a neutral dye [5] by periodate and oxidation of acridine yellow by chloramine-T [6]. Reports are also available on complex formation reaction of the iron (III) dimer with periodate ion [7] and the I-127 n.m.r. spectra of some transition-metal periodate complexes [8].…”

Section: Introductionmentioning

confidence: 98%

Manganese(II) catalyzed periodate oxidation of p-toluidine: a kinetic and mechanistic study

Kaushik

Kumar

et al. 2010

Reac Kinet Mech Cat

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“…A plot between log kcat vs l/D was found to be linear (Figure 4), with negative slope indicating that the reaction is an iondipolar type involving a direct bimolecular attack of p-anisidine on H4IO6 -or IO4 -(i.e. periodate monoanion which has been assumed to be the reactive species in the pH range in which the present studies were made, based on the evidences already available in literature [2,26]). Also, the negative slope is in accordance with Amis equation for ion-dipolar type reaction.…”

Section: Effect Of Ph Dielectric Constant Of the Medium And Free Radical Scavengersmentioning

confidence: 99%

Kinetics and Mechanism of Mn(II) Catalyzed Periodate Oxidation of p-anisidine: Effect of pH

Kaushik

Singh

Manila

et al. 2014

Bull. Chem. React. Eng. Catal.

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The stoichiometry for the initial part of the reaction, Mn II catalysed periodate oxidation of p-anisidine (PMA), has been found to be 1 mol of PMA consuming 2 mol of periodate ion. The kinetic-mechanistic study of reaction in acetone-water medium was made spectrophotometrically by noting the increase in the absorbance of reaction intermediate. Reaction is first order in reactants and catalyst each. A decrease in dielectric constant of the medium results in decrease in the rate of reaction suggesting an iondipole type interaction. Free radical scavengers do not affect the reaction rate. A special type of rate-pH profile shows a maximum at pH = 7.0. This pH effect also suggests the involvement of at least three differently reactive reactant species in the reaction and this fact has been considered by us while deriving the rate law. Under pseudo first order conditions [IO4 -] >> [PMA] and in agreement with the derived rate law, the 1/kcat versus [H + ] plot passes through the minimum and the results can be fitted to the equation:where kK3K4 is the empirical composite rate constant, Kw is ionic product of water, K2 is acid dissociation constant of H4IO6 -and Kb is base dissociation constant of PMA. The experimental value of [H + ]min is in good agreement with the value calculated by using the derived rate law equation and is characteristic of the substrate involved relating to the base dissociation constant of PMA. The value of thermodynamic parameters have been evaluated.

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“…There seems to be a literature contradiction about the dominating aqueous form of periodate ion (IO 4 − or H 4 IO 6 − ), [26][27][28][29][30] but this is seldom important from the view point of redox chemistry. 6…”

Section: Introductionmentioning

confidence: 99%

Kinetic studies of hydroxyquinone formation from water soluble benzoquinones

et al. 2014

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Table of contents entryThe kinetics of the reactions between 1,4-benzoquinones and hydrogen peroxide were studied.A systematic study of substituent effects revealed a Hammett-like correlation, where the rate of reaction is mainly determined by electronic effects. 3 AbstractThe kinetics and mechanisms of the redox reactions between hydrogen peroxide and 1,4-benzoquinone, 2-methyl-1,4-benzoquinone, 2,6-dimethyl-1,4-benzoquinone, 2-chloro-1,4-benzoquinone and 2,6-dichloro-1,4-benzoquinone were studied in aqueous media using spectrophotometric monitoring. The formation and decay of a hydroxylated 1,4-benzoquinone was detected. The formation of the intermediate was first order with respect to the parent 1,4-bezoquinone and hydrogen peroxide, whereas inverse first order dependence was revealed with respect to hydrogen ion. The decomposition reaction had two parallel pathways: one was first order with respect to the intermediate, while the other showed second-order dependence.The values of the rate constant measured for the formation step were successfully correlated with both the redox potentials of the substituted quinone/hydroquinone systems and the pK a values of the hydroxylated quinone derivatives. Therefore, electronic effects govern the reactivity of the quinones in this process. NMR and GC-MS measurements were carried out to identify the products in the system. Quantum mechanical calculations were also carried out in these systems.4

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Complex formation reaction of the iron(iii) hydroxo dimer with periodate ion

Cited by 17 publications

References 29 publications

Manganese(II) catalyzed periodate oxidation of p-toluidine: a kinetic and mechanistic study

Manganese(II) catalyzed periodate oxidation of p-toluidine: a kinetic and mechanistic study

Kinetics and Mechanism of Mn(II) Catalyzed Periodate Oxidation of p-anisidine: Effect of pH

Kinetic studies of hydroxyquinone formation from water soluble benzoquinones

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