Coordination of aza heterocycles with macroheterocyclic metal complexes in amphiprotic media: III. Kinetics and mechanism of inner-sphere ligand exchange in (tetraphenylporphyrinato)chromium(III)

Inner-sphere replacement of alcohols by imidazole and its derivatives in the complex (acetato)-(tetraphenylporphyrinato)chromium(III) was studied by electronic absorption spectroscopy. The rate constants and activation parameters of the process were calculated. The entering ligand structure was shown to affect the reaction rate, while the alcohol nature (departing ligand) does not influence the kinetic parameters of the process to an appreciable extent. Regression analysis revealed participation of imidazole and ethanol in the rate-determining stages. The kinetic equation for the inner-sphere axial substitution implies interaction of a free alcohol molecule with that coordinated to chromium, followed by replacement of the associate by the heteroring. Mathematical processing of the kinetic data in terms of the proposed solvolytic association-dissociation mechanism gave the rate constants for particular stages of the process and showed an extremal relation between the rate constant and composition of the solvent.     

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Kinetics and products of the reaction of diazo compounds with SO2

Data were obtained on the composition of products and kinetics of the reaction of SO₂ with Ph(R)CN₂ (R=Ph, Me) in solutions of isooctane, 1,4-di-oxane, and ethanol at 295 K. A mechanism was proposed for the process in accordance with which the sulfene being formed participates in concurrent reactions with the starting reagents. The relative rate constants for the process stages were determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2496–2500, November, 1990.