Anation kinetics of pentacyanoaquachromate(III) by thiocyanate and azide

The kinetics of the reaction of Cr(CN)₅(H₂O)²⁻ with NCS⁻ and were studied at pH 5.0 and at pH 6.3-7.0, respectively, as a function of the temperature between 25.0 and 55.0 °C, and at various ionic strengths. Anation occurs in competition with aquation of CN⁻, with rate constants that exhibit less-than-first-order dependence on the concentration of the entering anions. The results are interpreted in terms of ligand interchange in a context of association of the two reacting anions mediated by the Na⁺ or Ca²⁺ counterions. The degree of aggregation depends mainly on the total cationic charge rather than on the ionic strength, and is ca. 2-fold larger for than for NCS⁻. Within the associated species, is a better entering ligand than NCS⁻ by a factor of 4.5. The Cr(CN)₅(NCS)³⁻ and Cr(CN)₅(N₃)³⁻ complexes were also synthesized, and the rates of aquation of NCS⁻ and were measured at pH 5.0 and between 55.0 and 80.0 °C, over the same range of ionic strengths. The ionic strength enhances the anation rates but has little effect on the aquation rates. The average activation enthalpies of the interchange step are 80 ± 3 and 76 ± 3 kJ mol⁻¹ for entry of NCS⁻ and , respectively. Those of the corresponding aquation reactions are 94 ± 4 and 107 ± 4 kJ mol⁻¹. Within error limits, all ΔH^‡ values are independent of the ionic strength. The results are consistent with an I_d mechanism for substitution in Cr(CN)₅X^z− complexes.     

Kinetic studies of tris(2,2′-bipyridine)iron(III) perchlorate with cobaloxime, [Co(dmgBF2)2(H2O)2]

The kinetics of the reduction of by Co(dmgBF₂)₂(H₂O)₂ in 0.041 M HNO₃/NaNO₃ was found to be first-order in both the oxidizing and reducing agents and the second-order rate constant is given by k_obs = k₁ + k₂K[Cl⁻], with k₁=1.59 × 10⁶ M⁻¹ s⁻¹and k₂K = 1.83 × 10⁸ M⁻² s⁻¹, at 25 °C. The term that is first-order in [Cl⁻] is attributed to the formation of an ion-pair between and Cl⁻. For k₁, the activation parameters ΔH* and ΔS* are 2.22 ± 0.02 kcal mol⁻¹ and −22.7 ± 0.8 cal mol⁻¹ K⁻¹, respectively. The self-exchange rate constant of k₂₂ ≈ 8.7 × 10⁻³ M⁻¹ s⁻¹ for was estimated using Marcus theory and the known self-exchange rate constant for .