Octahedral cobalt(III) complexes in dipolar aprotic solvents. VI. Spectrophotometric determination of ion association of halide ions with cis-chlorodimethylformamidebisethylenediaminecobalt(III) ion and cis-chlorobromobisethylenediaminecobalt(III)ion in anhydrous NN-dimethylformamide

Using a spectrophotometric technique the ion association constants for three systems of octahedral cobalt complexes and halide ions have been determined at three temperatures in NN-dimethylformamide. The values of K, ΔH�, and ΔS� for each system have been calculated. At 30� they are as follows: cis-[CoCl(DMF) en2]2+ + Cl- ↔ ion pair K=1.51�0.03 x 104 1.mole-1(ΔH0= 0.93 � 0.02 kcal mole-1,ΔS�= 22.l+0.4 e.u) cis-[CoCl(DMF) en2]2++2Cl- ↔ ion triplet K= 1.21�0.05 X 106 1.2 mole-2(ΔH�=-3.8�0.lkcal mole-1, ΔS�=15.41� 0.5 e.u) cis-[CoCl(DMF) en2]2++Br- ↔ ion pair K= 9.20�0.18 X 103 1.1 mole-1(ΔH�=-7.2�0.lkcal mole-1, ΔS�=42� 1.0 e.u) cis-[CoBrCl en2]+ + Br- ↔ ion pair K = 690�l41. mole-1 (ΔH� = 1.27�0.03 kcal mole-1, ΔS�= 8.8�0.2 e.u.) The dependence of the measured K, the association constant, on the wavelength of measurement, small amounts of water in the solvent, and the anion of the complex salt, has also been investigated.