Thiadiazoloporphyrinoids. Coordination of hexa(4-tert-butylphenyl)-substituted trithiadiazoltripyrrol macrocycle with Ni(II) in DMF

Thiadiazoloporphyrinoids. Coordination of hexa(4-tert-butylphenyl)-substituted... 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Russian Journal of Coordination Chemistry Springer Journals

Thiadiazoloporphyrinoids. Coordination of hexa(4-tert-butylphenyl)-substituted trithiadiazoltripyrrol macrocycle with Ni(II) in DMF

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Publisher
Nauka/Interperiodica
Copyright
Copyright © 2006 by Pleiades Publishing, Inc.
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry
ISSN
1070-3284
eISSN
1608-3318
D.O.I.
10.1134/S107032840611011X
Publisher site
See Article on Publisher Site

Abstract

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.

Journal

Russian Journal of Coordination ChemistrySpringer Journals

Published: Nov 6, 2006

References

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