Abstract
The composition of the solvent cage of chloropentaamminechromium(III) ion was determined in water—dimethyl sulfoxide media using proton NMR line-broadening methods and the approach of Covington and coworkers. The number of solvent molecules in the solvent cage was found to be 10. The stepwise formation constants for the substitution of 10 water molecules by 10 dimethylsulfoxide molecules in this solvent cage were calculated. After the first such substitution each successive substitution becomes 1027 J mol −1 more difficult, exclusive of statistical factors, than the preceding substitution. The solvent cage composition was assumed to apply to the chloropentaamminecobalt(III) ion. Mercury(II)-assisted removal of chloride ion from the latter complex gave [Co(NH 3) 5{OSMe 2}] 3+/[Co(NH 3) 5(H 2O)] 3+ product ratios which did not correlate with either the solvent cage composition or the activity ratio of the two solvent components in the bulk phase of the solvent.
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