Reaction of cobalt(III) with sodium salicylate in aqueous perchloric acid

Sandberg, R. G.; Auborn, James J.; Eyring, Edward M.; Watkins, Kay O.

doi:10.1021/ic50114a048

Cited by 5 publications

(3 citation statements)

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“…These complexes are much weaker than the monocomplex formed by aquocobalt(III) with salicylic acid, where the dissociation rate constants in reactions 10 and 11 are too small to measure on the stopped-flow time scale . We estimate from the data in ref that K 1 for the monosalicylatocobalt(III) complex is at least 300 at 25 °C and an ionic strength of 1.5 M.…”

Section: Proposed Mechanismmentioning

confidence: 90%

“…3,5,6 In this limiting case, the rate of the overall process is controlled by the rate of formation of the intermediate inner-sphere complex [Co(III)B] aq , which amounts to substitution control of a redox reaction as a result of the comparative kinetic inertness of aquocobalt(III) and despite the strongly oxidizing character of the aquocobalt(III)/cobalt(II) couple, which might have favored outer-sphere mechanisms. 3,6 When k el , k -o in scheme 2, it may be possible to measure the rates of formation and dissociation of aquocobalt(III) complexes, as reported with Cl -(refs 7 and 8) and with malic, 9 thiomalic, 10,11 and salicylic 12 acids as reductants. The results obtained with these ligands are consistent with a substitutioncontrolled, inner-sphere mechanism for the aquocobalt(III) oxidation of oxalic acid.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics of Formation and Dissociation of Aquocobalt(III) Complexes with Some Carboxylic Acids in Acid Perchlorate Solution

Davies¹

2007

J. Phys. Chem. B

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The rates of formation and dissociation of monocarboxylic complexes of aquocobalt(III) cations with propionic, malonic, and 2-ethylmalonic acids have been measured with the stopped-flow method over a range of concentrations and temperatures in acid perchlorate media at an ionic strength 3.0 M. Although the rate constants for reactions of CoOHaq2+ with neutral ligands cover only a small range, indicating a dissociative mechanism, the associated activation parameters change cooperatively. These variations are discussed in terms of differences in the structure, proton distribution, and rates of water loss in the ion-pair precursors for the different ligands. Similar activation enthalpies of dissociation indicate a common mode of coordination, and the positive activation entropies for dissociation are consistent with a neutral leaving group.

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Section: Proposed Mechanismmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Kinetics of Formation and Dissociation of Aquocobalt(III) Complexes with Some Carboxylic Acids in Acid Perchlorate Solution

Davies¹

2007

J. Phys. Chem. B

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“…Intermediate cobalt(II1) species have been identified in several instances (6)(7)(8). In the present study, using [Co(III)], such interactions between oxidant and reductant would be expected to be weak and this enables the investigation of other factors in electron transfer reactions of this type.…”

mentioning

confidence: 87%

Metal-ion oxidations in solution. Part XXI. Kinetics and mechanism of the reaction of ascorbic acid, hydroquinone, and catechol with 12-tungstocobaltoate(III)

Amjad¹,

Brodovitch²,

McAuley³

1977

Can. J. Chem.

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. Can. J. Chem. 55, 3581 (1977).The mechanisms of oxidation of the three di-hydroxy substrates in the title reactions have been investigated in acid media [HCIO,] = 0.04-1.00 M, at an ionic strength of 1.0 M [LiCIO,] over the temperature range 5-35°C using the stopped-flow method. In contrast to the reactions of hydroquinone (k2(25"C) = 1.43 x 10, M -' s-' , AH* = 3.6 + 0.4 kcal mol-I, AS* = -34 + 8 cal deg-' mol-') and catechol (k2(25"C) = 9.5 x 1 0 2 M -' s-', AH* = 5.9 _+ 0.9 kcal mol-', AS* = 27 + 8 cal deg-I mol-I) where no hydrogen ion dependence is observed over the range studied, the rate variations of oxidation of ascorbic acid (H2A) are consistent with two reactions involving H2A (k, = 77.4 M -' s-I, AH* = 4.5 , 0.6 kcal niol-', AS* = -35 + 5 cal deg-I mol-') and HA-( k , = 2.41 x lo5 M -' s-' , AH* = 2.0 + 1 kcal mol-', AS* = -17 + 6 cal deg-I mol-I). The dissociation constant of ascorbic acid has been redetermined over the temperature range studied. Solvation effects are considered important in these outer-sphere systems, which may be discussed in terms of the Marcus relationship. Comparisons with related reactions are discussed.

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ChemInform Abstract: RK. VON KOBALT(III) MIT NATRIUMSALICYLAT IN WAESSRIGER PERCHLORSAEURE

Sandberg¹,

Auborn²,

Eyring³

et al. 1972

Chemischer Informationsdienst

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Reaction of cobalt(III) with sodium salicylate in aqueous perchloric acid

Cited by 5 publications

References 1 publication

Kinetics of Formation and Dissociation of Aquocobalt(III) Complexes with Some Carboxylic Acids in Acid Perchlorate Solution

Kinetics of Formation and Dissociation of Aquocobalt(III) Complexes with Some Carboxylic Acids in Acid Perchlorate Solution

Metal-ion oxidations in solution. Part XXI. Kinetics and mechanism of the reaction of ascorbic acid, hydroquinone, and catechol with 12-tungstocobaltoate(III)

ChemInform Abstract: RK. VON KOBALT(III) MIT NATRIUMSALICYLAT IN WAESSRIGER PERCHLORSAEURE

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