Equilibrium and kinetic study of imidazole binding to phthalocyaninatoiron(II) in dimethyl sulphoxide

Paolo Ascenzi, Maurizio Brunori, Giovanna Pennesi, Claudio Ercolani, Fabrizio Monacelli

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Abstract

The reaction between imidazole (Him) and phthalocyaninatoiron(II) [Fe(pc)] in dimethyl sulphoxide (dmso) has been studied, at 20 °C, from both equilibrium and kinetic points of view. In the presence of excess of Him the adduct [Fe(pc) (Him)2] is formed via two consecutive pseudo-first-order processes. The observed rate constants have the general form: kobs. = k1f[Him] + k1r with k1f′ = (9.8 ± 0.2) × 103 dm3 mol-1 s-1 and k1f″ = 5.4 ± 0.15 dm3 mol-1 s-1, for the binding of the first and second Him molecules, respectively. Equilibrium experiments yield K1′ = (6.4 ± 2.6) × 105 dm3 mol-1 and K1″ = (7.4 ± 0.5) × 103 dm3 mol-1 for the stepwise formation of the [Fe(pc) (dmso) (Him)] and [Fe(pc) (Him)2] adducts, respectively. From the values of the second-order rate constants (k1f′ and k1f″) and of the equilibrium constants (K1′ and K1″), the dissociation rate constants have been estimated to be k1r′ = 1.5 × 10-2 s-1 and k1r″ = 7.3 × 10-4 s-1. The results are discussed in the light of related previous studies.

Original languageEnglish
Pages (from-to)105-108
Number of pages4
JournalJournal of the Chemical Society, Dalton Transactions
Issue number1
DOIs
Publication statusPublished - 1990

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Dimethyl Sulfoxide
Rate constants
Kinetics
Equilibrium constants
Molecules
imidazole
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

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Equilibrium and kinetic study of imidazole binding to phthalocyaninatoiron(II) in dimethyl sulphoxide. / Ascenzi, Paolo; Brunori, Maurizio; Pennesi, Giovanna; Ercolani, Claudio; Monacelli, Fabrizio.

In: Journal of the Chemical Society, Dalton Transactions, No. 1, 1990, p. 105-108.

Research output: Contribution to journalArticle

Ascenzi, Paolo ; Brunori, Maurizio ; Pennesi, Giovanna ; Ercolani, Claudio ; Monacelli, Fabrizio. / Equilibrium and kinetic study of imidazole binding to phthalocyaninatoiron(II) in dimethyl sulphoxide. In: Journal of the Chemical Society, Dalton Transactions. 1990 ; No. 1. pp. 105-108.
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abstract = "The reaction between imidazole (Him) and phthalocyaninatoiron(II) [Fe(pc)] in dimethyl sulphoxide (dmso) has been studied, at 20 °C, from both equilibrium and kinetic points of view. In the presence of excess of Him the adduct [Fe(pc) (Him)2] is formed via two consecutive pseudo-first-order processes. The observed rate constants have the general form: kobs. = k1f[Him] + k1r with k1f′ = (9.8 ± 0.2) × 103 dm3 mol-1 s-1 and k1f″ = 5.4 ± 0.15 dm3 mol-1 s-1, for the binding of the first and second Him molecules, respectively. Equilibrium experiments yield K1′ = (6.4 ± 2.6) × 105 dm3 mol-1 and K1″ = (7.4 ± 0.5) × 103 dm3 mol-1 for the stepwise formation of the [Fe(pc) (dmso) (Him)] and [Fe(pc) (Him)2] adducts, respectively. From the values of the second-order rate constants (k1f′ and k1f″) and of the equilibrium constants (K1′ and K1″), the dissociation rate constants have been estimated to be k1r′ = 1.5 × 10-2 s-1 and k1r″ = 7.3 × 10-4 s-1. The results are discussed in the light of related previous studies.",
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N2 - The reaction between imidazole (Him) and phthalocyaninatoiron(II) [Fe(pc)] in dimethyl sulphoxide (dmso) has been studied, at 20 °C, from both equilibrium and kinetic points of view. In the presence of excess of Him the adduct [Fe(pc) (Him)2] is formed via two consecutive pseudo-first-order processes. The observed rate constants have the general form: kobs. = k1f[Him] + k1r with k1f′ = (9.8 ± 0.2) × 103 dm3 mol-1 s-1 and k1f″ = 5.4 ± 0.15 dm3 mol-1 s-1, for the binding of the first and second Him molecules, respectively. Equilibrium experiments yield K1′ = (6.4 ± 2.6) × 105 dm3 mol-1 and K1″ = (7.4 ± 0.5) × 103 dm3 mol-1 for the stepwise formation of the [Fe(pc) (dmso) (Him)] and [Fe(pc) (Him)2] adducts, respectively. From the values of the second-order rate constants (k1f′ and k1f″) and of the equilibrium constants (K1′ and K1″), the dissociation rate constants have been estimated to be k1r′ = 1.5 × 10-2 s-1 and k1r″ = 7.3 × 10-4 s-1. The results are discussed in the light of related previous studies.

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