The rate constants, partial orders in the reagent concentrations and activation parameters of interaction of macroheterocyclic compound based on consecutively alternating fragments of thiazole and 3,4-bis(4-tert-butylphenyl)pyrole (3 + 3) with dehydrated Ni(OAc)2 in dry DNF depending on the reagent concentrations and temperature were determined. Within a narrow range of the salt concentrations ((1.58−1.87) × 10−4 mol/l), the third-order equation of the reaction rate was obtained i.e., the first order in a macrocyclic ligand and the second order in a salt, which was interpreted in terms of the mechanism of a stepwise coordination with three [Ni(OAc)]+ ions that is reversible only at the second step. Because of the low solubility of McH3, the monomer-dimer equilibrium also becomes kinetically significant. The constant of McH3 dimerization in DMF at 298 K equal to 1.6 × 105 mol−1 was determined by spectrophotometric titration.
Russian Journal of Coordination Chemistry – Springer Journals
Published: Nov 6, 2006
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