Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Simulation Analysis of the Acid–catalyzed Hydrolysis of Carboxylatopentammineruthenium(III) Complexes
Katsutoshi OhkuboHiroyuki SakamotoFutoshi KitagawaAkira Ohyoshi
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1973 Volume 46 Issue 9 Pages 2651-2654

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Abstract

The mechanism of the acid-catalyzed hydrolysis of (NH3)5RuO2CR2+ (R=H, CH3, C2H5, (CH3)2CH, CH2OH, and/or CH2NH2) has been established by the trapezoidal simulation analyses with a computer. The proposed reaction sequences of SN1 combined with SN2 mechanisms involving a quasi-stable intermediate (NH3)5Ru3+ have proved to be plausible, and the kinetic parameters (rate constants, ΔH\ eweq, ΔS\ eweq, etc.) have been given for all of the elementary reactions. The aquation rate has been determined by the solvent-assisted, heterolytic dissociation of (NH3)5RuO2CR2+ and follows this order: formato>acetato>propionato>isobutyrato>glycolato>glycinato.

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