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Effects of solvents on the reactions of coordination complexes: Part 20. Kinetics and mechanism of base hydrolysis of (αβS) (Salicylato) (Tetraethylenepentamine) Cobalt(III) in aquo-organic solvent media

✍ Scribed by Anadi C. Dash; Guru C. Pradhan; Raghunath Acharya

Publisher
John Wiley and Sons
Year
1995
Tongue
English
Weight
595 KB
Volume
27
Category
Article
ISSN
0538-8066

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✦ Synopsis

The kinetics of base hydrolysis of (CUPS) (salicylato) (tetraethylenepentamine) cobalt(II1) have been investigated in aquo-organic solvent media at 15.0 f t, "C < 40.0, and I = 0.10 mol dm (C104-) using propane-2-01 (570% v/v), t-butanol(560% v/v), acetone (570% v/v, acetonitrile (550% v/v), and ethylene glycol (170% v/v) as cosolvents. Both the spontaneous and base-catalyzed hydrolysis of the phenoxide species [(tetren)CoOzCC~H40]+ were appreciably accelerated by the cosolvents Pr'OH, ButOH, MeZCO, and MeCN. On the contrary the base hydroylsis (kz) was retarded while spontaneous aquation (kl) was accelerated to a small extent with increased EG content. Variation of log k l and log k; (k; = kz at I = 0) with mole fraction (x0.s) or reciprocal of the relative permitivity (Dkl) of the media were nonlinear. The transfer free energy of the transition state relative to that of the initial state of the substrate for transfer of species from water to mixed solvents also varied nonlinearly with xo.s, or D l l indicating solvent specificity. The activation parameters, AH # and ASf varied nonlinearly with solvent composition exhibiting extrema.

The preferential solvation and solvent structural effects mediated the kinetics and energetics of the reaction.

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