Study of the base‐catalyzed nitrito–nitro isomerization reaction ([(NH3)5Co‐ONO]2+ → [(NH3)5Co‐NO2]2+) in mixed solvents |
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| Authors: | R Jimnez M Villar M Cueto E Grueso J Illanes J I Cobrian F Cantn I Villa J M Snchez S Maza J M Muoz C Muoz R Prado‐Gotor |
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| Institution: | R. Jiménez,M. Villar,M. Cueto,E. Grueso,J. Illanes,J. I. Cobrian,F. Cantón,I. Villa,J. M. Sánchez,S. Maza,J. M. Muñoz,C. Muñoz,R. Prado‐Gotor |
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| Abstract: | The base‐catalyzed linkage isomerization of Co(NH3)5‐ONO]2+ to the nitro (NH3)5Co‐NO2]2+ form is studied in various isodielectric water–cosolvent mixtures (methanol, ethanol, tert‐butyl alcohol, and 2‐propanol) at 298 K. In all cases, except for methanol–water mixtures, the rate constants increase with the proportion of cosolvent. Medium effects have been rationalized by using a multiparameter regression of solvent parameters which rationalizes the results obtained, including water–methanol mixtures. The experimental data, k2, in fact, are well correlated through the following equation: ![equation image]( "equation image") where A, B, and Gexc are the acidity parameter, the basicity parameter, and the excess Gibbs free energy of the mixture, respectively. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 410–415, 2004 |
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