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Kinetics of the solvolysis of [Co(3Rpy)4Cl2]+ (R = Me or Et) in water + propan-2-ol mixtures

✍ Scribed by Gehan M. El-subruiti; Cecil F. Wells; Ibrahim M. Sidahmed

Publisher
John Wiley and Sons
Year
1991
Tongue
English
Weight
639 KB
Volume
23
Category
Article
ISSN
0538-8066

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✦ Synopsis

Rates of solvolysis of complex ions [C0(3Rpy)~Cl~]+ with R = Me and Et have been determined in mixtures of water with the hydrophobic co-solvent propan-2-01 for a range of temperatures. The variations of the enthalpies and entropies of activation with the solvent composition have been correlated with the physical properties of the solvent and it has been shown that the linear plot found for AH* against AS* in water + propan-2-01 is coincident with that found for water + methanol mixtures. A free energy cycle has been applied to the dissociative-type process of initial state (C"') going to the transition state (M("+')'. . . . . C1-) using values for the free energy of transfer of the chloride ion from water into the mixture, AGP(Cl-), derived from the solvent sorting technique or from the TATB/TPTB method. Irrespective of the source of AGP(Cl-), it is found that A G P ( C O ( ~R ~~) ~C ~" * ) ca. A G P ( C O ( ~R ~~) ~C ~~+ ) (where * indicates a species in the transition state) for mol fractions of propan-2-01 x z 2 0.04-0.05 with A G P ( C O ( ~R ~~) ~C ~~' * ) becoming increasingly more negative than AGP(Co(3Rpy)4C12') as xz increases above 0.05. These variations are compared with those for the solvolysis of the same ions in water + methanol mixtures and of a range of other ions in water + propan-2-01 mixtures.

It is concluded that, using values for AGp(Cl-) from either source, the stabilizing influence of changes in solvent structure is greater on the cation in the transition state than on the cation in the initial state for the solvolyses of complexes [ C ~( R p y ) ~C l ~+ l and [CoenzLCl]"'.

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