Kinetic and equilibrium properties of ...

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Title Kinetic and equilibrium properties of pentacyano(3,5-dimethylpyridine)-iron(II) and related anions in mixed aqueous solvents
Author(s) M. J. Blandamer, J. Burgess, Robert I. Haines
Journal Journal of the Chemical Society, Dalton Transaction
Date 1976
Volume
Issue 14
Start page 1293
End page 1298
Abstract The kinetic pattern for reaction of [Fe(CN)5(3,5-Me2py)]3? and [Fe(CN)5,(3-CNpy)]3? with a range of incomlng groups, in water and in 40% glycol and 40% t-butyl alcohol, is consistent with the operation of a D mechanism under all the conditions studied. Rate constants for the reaction of [Fe(CN)5,(3.5-Me2py)]3? with cyanide ion have been determined in binary aqueous mixtures containing up to 40% by volume of methanol, ethanol, t-butyl alcohol, glycerol, or tetrahydrofuran. Correlation of these rate constants with Grunwald?Winstein Y values gives a value of m of ?0.1; this small value reflects the low sensitivity of the rate to solvent composition. Free energies of activation determined from the observed rate constants have been plotted against excess Gibbs free energies of mixing (GE) for the respective solvent mixtures. The resulting pattern indicates how far the thermodynamic characteristics of mixing of the solvent are reflected in the kinetics of this substitution reaction. The relation between the relative stabilities of [Fe(CN)5(3,5-Me2py)]3? and its pyridine analogue, and solvent mixture GE values, has also beenexamined. Thesolvatochromic behaviourofthecharge-transfer band of [Fe(CN)5,(N-methylpyrarinium)]2? has been investigated, and contrasted with that of organic analogues.
DOI 10.1039/DT9760001293
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