Solvent and pressure effects on kinetics of substitution at pentacyanoferrate(II) anions

Blandamer, Michael J.; Burgess, John; Morcom, K. W.; Sherry, Robert

doi:10.1007/bf00618572

Cited by 23 publications

(6 citation statements)

References 28 publications

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“…It is concluded that the substitution reaction between [Fe(CN) 5 H 2 O] 3 À and INH in acidic medium, to yield [Fe(CN) 5 INH] 3 À , l max 435 nm, which corresponds to a metal-to-ligand charge-transfer band. Activation parameters are provided in support of the proposed mechanism.…”

Section: Resultsmentioning

confidence: 97%

“…The kinetics of the reaction were studied spectrophotometrically by monitoring the increase in absorbance at 435 nm, the l max of the product [Fe(CN) 5 INH] 3 À (Figure 3). In all experiments the initial molar concentration of ligand was at least a 10 fold excess over that of the initial molar concentration of [Fe(CN) 5 H 2 O] 3 À , to ensure pseudo-first-order conditions.…”

Section: Kinetic Measurementsmentioning

confidence: 99%

“…The slope of the plot gives the values of k f ¼ k ap . 5 OH 2 ] (AQP) was stored in a dark amber-coloured bottle to avoid photodecomposition and oxidation. The pH of the reaction mixture was maintained at 3.8 + 0.02, using phthalate-sodium hydroxide buffer solution.…”

Section: Mechanismmentioning

confidence: 99%

“…In the present paper, the results of a kinetic study of the ligand substitution reaction of aquapentacyanoferrate(II) by INH at 435 nm (l max of [Fe(CN) 5 …”

Section: Introductionmentioning

confidence: 99%

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Kinetics and Mechanism of Formation of [Fe(Cn)₅Inh]^3- by Ligand Substitution in Acidic Media (Inh = Isoniazid)

Naik

Kumar

2012

Progress in Reaction Kinetics and Mechanism

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The kinetics and mechanism of formation of [Fe(CN) 5 INH] 3 À by a ligand substitution reaction between aquapentacyanoferrate(II) ion and isoniazid, (pyridine-4-carboxylic acid hydrazide) (INH) have been investigated spectrophotometrically in acidic media at 435 nm (l max of product), under pseudo-first order conditions, using excess of INH over [Fe(CN) 5 H 2 O] 3 À . The reaction was studied as a function of [Fe(CN) 5 H 2 O 3 À ], [INH], pH, ionic strength and temperature, by varying only one of these variables while other variables were held constant. The reaction exhibited first-order kinetics in [INH] while it was independent of [Fe(CN) 5 H 2 O 3 À ] in the chosen concentration range. The effect of temperature on the reaction rate yielded the activation parameters. The most plausible mechanism consistent with the experimental results has been proposed.

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Section: Resultsmentioning

confidence: 97%

Section: Kinetic Measurementsmentioning

confidence: 99%

Section: Mechanismmentioning

confidence: 99%

“…In the present paper, the results of a kinetic study of the ligand substitution reaction of aquapentacyanoferrate(II) by INH at 435 nm (l max of [Fe(CN) 5 …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Kinetics and Mechanism of Formation of [Fe(Cn)₅Inh]^3- by Ligand Substitution in Acidic Media (Inh = Isoniazid)

Naik

Kumar

2012

Progress in Reaction Kinetics and Mechanism

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“…This analysis is set out in Table 3 and illustrated in Figure 4. The small change in rate constant on going from water to 40% methanol arises from small changes in chemical potentials -here there is not the compensation between large but similar medium effects on initial and transition states that is such a striking feature of, e.g., substitution at pentacyanoferrates(II) [34]. The great increase in rate constant on going from water to 60% DMSO can be ascribed to a combination of a marked decrease in chemical potential of the transition state and a modest increase in the chemical potential of the initial state, in turn the resultant of a large stabilisation of the complex outweighed by a larger destabilisation of hydroxide.…”

Section: Discussionmentioning

confidence: 99%

Solvation of iron(II) complexes of hexadentate tris-diimine Schiff base tripod ligands in alcohol?water and DMSO?water mixtures

Alousy

Burgess

Elvidge

2005

Transition Met Chem

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Solubilities of the perchlorate salt of the iron(II) complex of the tripodal ligand derived from tris(2-aminoethyl)amine and pyridine 2-carboxaldehyde, [Fe(fpyHg 3 tren)](ClO 4 ) 2 , have been determined in MeOH-, i-PrOH-, t-BuOH-, and DMSO-H 2 O mixtures. Solubilities of [Fe(fpyMeg 3 tren)](ClO 4 ) 2 and of [Fe(fpyPhg 3 tren)](ClO 4 ) 2 , analogues derived from 2-acetylpyridine and 2-benzoylpyridine, respectively, have been determined in MeOH-H 2 O mixtures. Transfer chemical potentials for the three complexes have been calculated from these solubilities, and solvation trends for these complexes discussed in relation to the overall pattern for iron(II)-diimine complexes in binary aqueous solvent mixtures. The crystal structure of [Fe(fpyHg 3 tren)](ClO 4 ) 2 has been determined.

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Mechanistic Studies on the Activation of NO by Iron and Cobalt Complexes

2007

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In this review, the reactions of nitric oxide with selected Fe and Co complexes of biological and environmental importance are reviewed. Fundamental chemical kinetics and mechanisms of reactions that lead to the formation and decay of nitrosyl complexes are illustrated and discussed on the basis of studies on Fe II and the release of NO from metal complexes and on the nature of the stable metal-NO complexes produced in solution.As will be seen for most of the presented reactions, the interaction of NO with the metal complex involves activation of the small NO molecule so that charge transfer occurs as a result of the formation of the metal-NO bond.

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Solvent and pressure effects on kinetics of substitution at pentacyanoferrate(II) anions

Cited by 23 publications

References 28 publications

Kinetics and Mechanism of Formation of [Fe(Cn)₅Inh]^3- by Ligand Substitution in Acidic Media (Inh = Isoniazid)

Kinetics and Mechanism of Formation of [Fe(Cn)₅Inh]^3- by Ligand Substitution in Acidic Media (Inh = Isoniazid)

Solvation of iron(II) complexes of hexadentate tris-diimine Schiff base tripod ligands in alcohol?water and DMSO?water mixtures

Mechanistic Studies on the Activation of NO by Iron and Cobalt Complexes

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Solvent and pressure effects on kinetics of substitution at pentacyanoferrate(II) anions

Cited by 23 publications

References 28 publications

Kinetics and Mechanism of Formation of [Fe(Cn)5Inh]3- by Ligand Substitution in Acidic Media (Inh = Isoniazid)

Kinetics and Mechanism of Formation of [Fe(Cn)5Inh]3- by Ligand Substitution in Acidic Media (Inh = Isoniazid)

Solvation of iron(II) complexes of hexadentate tris-diimine Schiff base tripod ligands in alcohol?water and DMSO?water mixtures

Mechanistic Studies on the Activation of NO by Iron and Cobalt Complexes

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Kinetics and Mechanism of Formation of [Fe(Cn)₅Inh]^3- by Ligand Substitution in Acidic Media (Inh = Isoniazid)

Kinetics and Mechanism of Formation of [Fe(Cn)₅Inh]^3- by Ligand Substitution in Acidic Media (Inh = Isoniazid)