Studies on outer sphere electron transfer reactions of some surfactant-cobalt(III) complexes with ferrocyanide anion

Sasikala, K.; Arunachalam, S.

doi:10.1134/s1061933x10040149

Cited by 9 publications

(5 citation statements)

References 32 publications

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“…The catalytic and inhibitory effect on the rate of the reaction by the added ions is possibly due to the absence of a bridged intermediate at the activated complex, such that the closeness of approach of the reactant ions in the activated complex is such as to allow the intervention of added ion. In view of this fact, influence of reaction rate by added ions is a characteristic of an outersphere mechanism, were most of the reactant ions maintain their coordination integrity in the activated complex prior to and during electron transfer [25][26][27][28]. • Polymerisation test involving addition of acrylamide to the partially reduced reaction mixture followed by excess methanol produced a gelatinous precipitate.…”

Section: Other Kinetic Data Determinedmentioning

confidence: 99%

Electron Transfer Reaction of Tris(1,10-phenanthroline)cobalt(III) Complex and Iodide Ion in An Aqueous Acidic Medium

2020

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Section: Other Kinetic Data Determinedmentioning

confidence: 99%

Electron Transfer Reaction of Tris(1,10-phenanthroline)cobalt(III) Complex and Iodide Ion in An Aqueous Acidic Medium

2020

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“…Micelle‐forming properties and electron‐transfer reactions of many surfactant metal complexes of similar nature to ordinary systems have been studied in our laboratories for a long time . In all these surfactant–metal complexes, the coordination complex containing a central metal ion with surrounding ligands coordinated to metal acts as a surfactant.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Thermodynamics of Formation and Electron‐Transfer Reactions of Surfactant Cobalt(III) Complexes Containing Polypyridyl Ligands with Fe(CN)₆⁴⁻in Microheterogeneous Environment

Nagaraj

Murugan²,

Thangamuniyandi

et al. 2015

Int J of Chemical Kinetics

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The electron‐transfer reaction of some surfactant cobalt(III) complexes, cis‐[Co(ip)2(C12H25NH2)2]3+ 1, cis‐[Co(dpq)2(C12H25NH2)2]3+ 2, and cis‐[Co(dpqc)2(C12H25NH2)2]3+ 3 (ip = imidazo[4,5‐f][1,10]phenanthroline, dpq = dipyrido[3,2‐d:2′‐3′‐f]quinoxaline, dpqc = dipyrido[3,2‐a:2′,4′‐c](6,7,8,9‐tetrahydro)phenazine, C12H25NH2 = dodecylamine) with the Fe(CN)64− ion has been investigated in microheterogeneous media (micelles, β‐cyclodextrin) at different temperatures by the spectrophotometric method under pseudo‐first‐order conditions using an excess of the reductant. Experimentally, the reaction was found to be second order and the electron transfer postulated as an outer sphere. The rate constant for the electron‐transfer reaction in micelles was found to increase with an increase in the initial concentration of the surfactant–cobalt(III) complex. This peculiar behavior of dependence of the second‐order rate constant on the initial concentration of one of the reactants has been attributed to the presence of various concentrations of micelles under different initial concentrations of the surfactant–cobalt(III) complex in the reaction medium. Inclusion of the long aliphatic chain of the surfactant complex ion into β‐cyclodextrin leads to decrease in the rate constant. Kinetic data and activation parameters are interpreted in terms of an outer‐sphere electron‐transfer mechanism. All these results have been interpreted in terms of the hydrophobic effect and the reactants with the opposite charge.

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“…The micelle-forming properties and electron transfer reactions of many surfactant metal complexes have been studied in our laboratory. [13][14][15][16] Recently, we reported on the outer-sphere electron transfer reactions between cis-[Co(en) 2 -(C 12 H 25 NH 2 ) 2 ](ClO 4 ) 3 , cis-[Co(trien)(C 12 H 25 NH 2 ) 2 ](ClO 4 ) 3 and iron(II) in micelles formed by these complexes themselves. 17,18 In all these surfactant metal complexes a coordination complex containing a central metal ion with surrounding ligands coordinated to the metal acts as a surfactant.…”

Section: Introductionmentioning

confidence: 99%

A comparative study on the electron transfer reaction (ETR) of surfactant cobalt(iii) complexes of aliphatic/aromatic ligands in micro heterogeneous media: a thermodynamic approach

et al. 2015

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The kinetics of electron transfer reaction (ETR) between the surfactant cobalt(III) complex ion, Cis-[Co(ip) 2 (C 12 H 25 NH 2 ) 2 ](ClO 4 ) 3 , Cis-[Co(dpq) 2 (C 12 H 25 NH 2 ) 2 ](ClO 4 ) 3 and Cis-[Co(dpqc) 2 (C 12 H 25 NH 2 ) 2 ](ClO 4 ) 3 (ip = imidazo [4,5-f][1,10]phenanthroline, dpq = dipyrido[3,2-d:2'-3'-f]quinoxaline, dpqc = dipyrido [3,2-a:2',4'-c](6,7,8,9-tetrahydro)phenazine, 5 C 12 H 25 NH 2 =dodecylamine) and Fe 2+ ion in micelles as well as β-cyclodextrin (β-CD) were studied at different temperatures by spectrophotometric method under pseudo first order conditions using an excess of the reductant. The results of surfactant complex containing aromatic ligands ETR higher than that of aliphatic ligands due to the results have been explained based on the hydrophobic effect. Experimentally the reactions were found to be second order and the electron transfer postulated as outer sphere. The rate constant increases with increase in the concentration of micelles but inclusion of the long aliphatic chain of the 10 surfactant cobalt(III) complexes into β-cyclodextrin decreases the rate of the reaction. Thermodynamic parameters were evaluated. 30 great deal of interest [9,10] because of their potential to prolong the lifetime of charge-transfer states, a goal of electron-transfer studies aiming to utilize solar energy [11]. Majumdar and Mahapatra [12] studied the electron transfer reactions between cobalt(III) and iron(II) complexes in cationic micellar medium (N-cetyl-N,N,N trimethyl ammonium bromide) and also in reverse micellar medium. The rate of the reaction was found to mainly depend on the inter-phase environment of the micelles and reverse micelles. Micelle-forming properties and electron transfer reactions of many surfactant metal complexes have been studied in our 35 laboratory [13-16]. Recently, we have reported on the outer-sphere electron transfer reactions between cis-[Co(en) 2 (C 12 H 25 NH 2 ) 2 ](ClO 4 ) 3, cis-[Co(trien)(C 12 H 25 NH 2 ) 2 ](ClO 4 ) 3 and iron(II) in the micelles formed by these complexes [Co(dpqc) 2 (C 12 H 25 NH 2 ) 2 ](ClO 4 ) 3 used as oxidants were prepared as reported by us earlier [34]. A stock solution of Fe(ClO 4 ) 2 was prepared by dissolving pure iron powder in slight excess of perchloric acid. The concentration of Fe 2+ ion was determined by a method similar to that reported in the literature [35] the ionic strength of the solution was adjusted by the addition of sodium 30 perchlorate solution. Kinetic measurementsThe rate of the reaction was measured spectrophotometrically using a Shimadzu -1800 UV-Visible spectrophotometer equipped with water Peltier system (PCB 150). The temperature was controlled within ± 0.01 0 C. A solution containing the desired concentration of β-cyclodextrin and surfactant cobalt(III) complexes in oxygen-free water was placed in a 1-cm cell, which was 35 then covered with a serum cap fitted with a syringe needle. This cell was placed in a thermostated compartment in the spectrophotometer and then the solution containing Fe 2+ was added a...

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Studies on outer sphere electron transfer reactions of some surfactant-cobalt(III) complexes with ferrocyanide anion

Cited by 9 publications

References 32 publications

Electron Transfer Reaction of Tris(1,10-phenanthroline)cobalt(III) Complex and Iodide Ion in An Aqueous Acidic Medium

Electron Transfer Reaction of Tris(1,10-phenanthroline)cobalt(III) Complex and Iodide Ion in An Aqueous Acidic Medium

Kinetics and Thermodynamics of Formation and Electron‐Transfer Reactions of Surfactant Cobalt(III) Complexes Containing Polypyridyl Ligands with Fe(CN)₆⁴⁻in Microheterogeneous Environment

A comparative study on the electron transfer reaction (ETR) of surfactant cobalt(iii) complexes of aliphatic/aromatic ligands in micro heterogeneous media: a thermodynamic approach

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Studies on outer sphere electron transfer reactions of some surfactant-cobalt(III) complexes with ferrocyanide anion

Cited by 9 publications

References 32 publications

Electron Transfer Reaction of Tris(1,10-phenanthroline)cobalt(III) Complex and Iodide Ion in An Aqueous Acidic Medium

Electron Transfer Reaction of Tris(1,10-phenanthroline)cobalt(III) Complex and Iodide Ion in An Aqueous Acidic Medium

Kinetics and Thermodynamics of Formation and Electron‐Transfer Reactions of Surfactant Cobalt(III) Complexes Containing Polypyridyl Ligands with Fe(CN)64−in Microheterogeneous Environment

A comparative study on the electron transfer reaction (ETR) of surfactant cobalt(iii) complexes of aliphatic/aromatic ligands in micro heterogeneous media: a thermodynamic approach

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Kinetics and Thermodynamics of Formation and Electron‐Transfer Reactions of Surfactant Cobalt(III) Complexes Containing Polypyridyl Ligands with Fe(CN)₆⁴⁻in Microheterogeneous Environment