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Mono‐complex formation kinetics of iron(III) with nonsubstituted octane and nonane 2,4‐dicarbonyl ligands in aqueous solution
Author(s) -
Blanco Carlos A.,
Romero Jose M.,
Verdu Jesus
Publication year - 1993
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550251204
Subject(s) - chemistry , ionic strength , aqueous solution , tautomer , reaction rate constant , kinetics , nonane , ligand (biochemistry) , medicinal chemistry , equilibrium constant , octane , inorganic chemistry , computational chemistry , organic chemistry , biochemistry , physics , receptor , quantum mechanics
The kinetics and mechanism of the reaction of complexation of iron(III) with 2,4‐octanedione and 2,4‐nonanedione have been investigated spectrophotometrically in aqueous solution at 10°C and ionic strength 0.5 mol dm −3 NaClO 4 . The equilibrium constants of the mono‐complexes have been determined. The mechanism proposed to account for the kinetic data involves a double reversible pathway where both Fe 3+ and Fe(OH) 2+ react with the enol tautomer of the ligand. 2,4‐Octanedione reacts with Fe 3+ and Fe(OH) 2+ with rate constants of 0.65 dm 3 mol −1 s −1 , and 14.07 dm 3 mol −1 s −1 , respectively. For 2,4‐nonanedione complexation the rate constants determined are 0.49 dm 3 mol −1 s −1 , and 11.39 dm 3 mol −1 s −1 , respectively. Some discussions are made on the basis of Eigen‐Wilkins theory considering the effect of solvent exchange on the complex formation. © 1993 John Wiley & Sons, Inc.