ChemInform Abstract: ELECTRON TRANSFER TO TRANS‐DIHYDROXOTETRAOXOOSMATE(VIII). II. KINETICS OF THE E OXIDATION OF DIMETHYL SULFOXIDE IN AQUEOUS ALKALINE MEDIA

Neogi, G.; Acharya, S.; Panda, R. K.; Ramaswamy, D.

doi:10.1002/chin.198401112

Cited by 2 publications

(4 citation statements)

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“…The oxidation product of S, which was orange yellow in solution, also did not complicate kinetic measurements for at least three half-lives of the reaction. The rate constant for the proton-assisted decomposition of Ni(1V) was negligible [2] in comparison with the kobs of the redox reaction under the employed conditions of the investigation. The monitoring wavelength (440-480-nm range) or a nitrogen atmosphere (in representative runs) did not practically influence the values Of hobs.…”

Section: Kinetic Proceduresmentioning

confidence: 91%

“…The data on proton-assisted decomposition of the Ni(1V) complex [2] have suggested that the first (outside) protonation of Ni(dmg)g-leads to an intramolecular hydrogen bonding (0-H---0) between dioximate oxygens of two ligands, without causing much alteration in the c.f.s.e. of the original pseudo-octahedral Ni(1V) complex.…”

Section: (6)mentioning

confidence: 98%

“…The stoichiometry data could not be collected at lower pH values since the acid decomposition of Ni(1V) interfered with the measurements [2]. Nor could the stoichiometric data be collected under conditions of [ In another set of experiments at pH 7.5,8.7, and 9.9, a solution of Ni(1V) (0.2 mol, 50 mL) was reacted with a solution of the substrate (0.02 mol, 50 mL).…”

Section: Stoichiometry and Productsmentioning

confidence: 99%

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Studies in nickel(IV) chemistry. Part 6. Kinetics of electron transfer from phenylhydrazine to tris‐(dimethylglyoximato) nickelate(IV) in aqueous medium

Acharya¹,

Neogi²,

Panda³

et al. 1982

Int J of Chemical Kinetics

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The kinetics of electron transfer from phenylhydrazine(S) to tris-(dimethylglyoximato) nickelate(IV), Ni(dmg)i-(dmg2-= dimethylglyoximate dianion), have been studied in aqueous medium in the range of 6.21 I pH I 12.2. The kinetics exhibit a pseudo-first-order disappearance of Ni(dmg)g-when excess S is present. The pseudo-first-order rate constants hobs are almost linearly dependent on [S]o for varying concentrations of the reductant. At constant [S]O, the k,b,-pH profile is U shaped. The kob values register a decrease as the [H+] is increased in the pH range of -12.2-9.5, remain almost constant (minimum) in the range of -9-8, and then again linearly increase as [H+] is increased in the pH range of -7-6.21. Results are interpreted in terms of a probable mechanism involving outer-sphere electron transfer from the phenylhydrazine and phenylhydrazinium cation species to the unprotonated and one-protonated species of the Ni(IV) complex. The reduction rate appears to be dependent on the nature of the species (unprotonated and one-protonated) of the oxidant Ni(IV) complex. The phenylhydrazinium cation reduces the Ni(IV) complex at least one order of magnitude faster than does the neutral reductant species. The major product of the oxidation of phenylhydrazine by the Ni(IV) complex is 4-hydroxyazobenzene with a small amount of phenol.

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Section: Kinetic Proceduresmentioning

confidence: 91%

Section: (6)mentioning

confidence: 98%

Section: Stoichiometry and Productsmentioning

confidence: 99%

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Studies in nickel(IV) chemistry. Part 6. Kinetics of electron transfer from phenylhydrazine to tris‐(dimethylglyoximato) nickelate(IV) in aqueous medium

Acharya¹,

Neogi²,

Panda³

et al. 1982

Int J of Chemical Kinetics

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“…We have recently carried out mechanistic investigations on oxidations of thiosulfate [8] and thiocyanate [9] by the oxohydroxoosmate(VII1) complex in alkaline media. The results in the case of thiosulfate oxidation [8] revealed that the electron transfer was substitution controlled.…”

Section: Introductionmentioning

confidence: 99%

Electron transfer to trans‐dihydroxotetraoxoosmate(VIII). II. Kinetics of the oxidation of dimethylsulfoxide in aqueous alkaline media

Neogi

Acharya

Panda

et al. 1983

Int J of Chemical Kinetics

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The kinetics of the oxidation of dimethylsulfoxide by oxohydroxoosmate(VII1) complex ions in alkaline media follow pseudo-first-order disappearance in Os(VII1). The values of the observed pseudo-first-order rate constant are linearly dependent on initial dimethylsulfoxide concentrations in a fortyfold range, and increase with increasing [OH-], leveling off at higher relative [OH-]. The results are interpreted in terms of outer sphere interactions involving dimethylsulfoxide and various species of the Os(VII1) complex. The more nucleophilic dihydroxotetraoxoosmate(VII1) ion reacts about 50 times faster than the trihydroxotrioxoosmate(VII1) species.

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ChemInform Abstract: ELECTRON TRANSFER TO TRANS‐DIHYDROXOTETRAOXOOSMATE(VIII). II. KINETICS OF THE E OXIDATION OF DIMETHYL SULFOXIDE IN AQUEOUS ALKALINE MEDIA

Cited by 2 publications

References 1 publication

Studies in nickel(IV) chemistry. Part 6. Kinetics of electron transfer from phenylhydrazine to tris‐(dimethylglyoximato) nickelate(IV) in aqueous medium

Studies in nickel(IV) chemistry. Part 6. Kinetics of electron transfer from phenylhydrazine to tris‐(dimethylglyoximato) nickelate(IV) in aqueous medium

Electron transfer to trans‐dihydroxotetraoxoosmate(VIII). II. Kinetics of the oxidation of dimethylsulfoxide in aqueous alkaline media

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