Micellar effects upon the reactions of complex ions in solution. Part 4.—Kinetics of aquation and base hydrolysis of some cis-(chloro)(amine)bis(ethylenediamine)cobalt(III) complexes in the presence of neutral and anionic surfactants in an aqueous medium

Abstract

The binding of the substrates cis-[Co(en)₂BCl]²⁺(en = 1,2-diaminoethane, B = alkylamines, imidazole, N-methylimidazole) to the micellar surface of sodium dodecyl sulphate resulted in the retardation of their dissociative aquation rates, the effect being sensitive to the hydrophobicity of the nonlabile amine ligand B. A contrastingly small rate acceleration for the corresponding ethanolamine and propan-2-ol amine complexes was observed under similar conditions. Triton X-100 (0.02 ⩽[Triton X]_T/mol dm^–3⩽ 0.1) had virtually no effect on the aquation rates of such complexes except for cis-[Co(en)₂(C₆H₁₁NH₂)Cl]²⁺, in which case a small rate retardation was also observed. The rates of base hydrolysis of the cobalt(III) substrates were strongly retarded by the anionic micelles of SDS; the neutral micelles of Triton X-100 were effective in decelerating the rate of base hydrolysis of the cyclohexylamine complex cis-[Co(en)₂(C₆H₁₁NH₂)Cl]²⁺ only. The pseudo-phase ion-exchange equilibrium model satisfactorily explained the binding of the cationic substrates to the anionic micellar pseudo-phase of SDS. The values of the ion-exchange equilibrium constant and the relative base hydrolysis rates (k^W/k^M) indicated that both micellar binding and retardation of hydrolysis are governed by hydrophobic and electrostatic interactions.