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@article{769274, author = {Lubal, Přemysl and AlbrechtandGary, AnneandMarie and Blanc, Silvie and Costa, Judite and Delgado, Rita}, article_location = {Prague}, article_number = {2}, keywords = {Copper(II) complexes; Pendant acetate arms; Tetraaza-macrocyclic ligands; Aza-crown macrocycles; Pyridinylbackbone}, language = {eng}, issn = {0010-0765}, journal = {Collection of Czechoslovak Chemical Communications}, title = {KINETIC AND MECHANISTIC STUDY OF DISSOCIATION OF COPPER(II) COMPLEX WITH 14-MEMBERED TETRAAZAMACROCYCLE LIGAND CONTAINING PYRIDINE AND N-CARBOXYMETHYL ARMS}, volume = {73}, year = {2008} }
TY - JOUR ID - 769274 AU - Lubal, Přemysl - Albrecht-Gary, Anne-Marie - Blanc, Silvie - Costa, Judite - Delgado, Rita PY - 2008 TI - KINETIC AND MECHANISTIC STUDY OF DISSOCIATION OF COPPER(II) COMPLEX WITH 14-MEMBERED TETRAAZAMACROCYCLE LIGAND CONTAINING PYRIDINE AND N-CARBOXYMETHYL ARMS JF - Collection of Czechoslovak Chemical Communications VL - 73 IS - 2 SP - 258-274 EP - 258-274 PB - Inst Org Chem Biochem Czech Acad Sci SN - 00100765 KW - Copper(II) complexes KW - Pendant acetate arms KW - Tetraaza-macrocyclic ligands KW - Aza-crown macrocycles KW - Pyridinylbackbone N2 - The kinetics of acid-catalyzed dissociation of the copper(II) complex with 7-methyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene-3,11-diacetic acid (ac2Me[14]pyN4) at [H+] = 0.05-0.25 M, I = 0.25 M (Na, H)ClO4, and T = 298.16 K was studied with conventional and stopped-flow UV/VIS spectroscopy. Three steps of consecutive complex reaction were observed. The very fast first and second steps characterized by k1 = 70 +/- 10 and k2 = 0.23 +/- 0.01 M-1 s-1 depend on the H+ concentration. The third step is very slow, k3 = (1.08 +/- 0.03) * 10-3 s-1, and does not depend on the H+ concentration. Latter rate-determining step involves an isomerisation process forcing the copper(II) ion to leave rapidly the macrocyclic cavity. The reaction mechanism of the complex dissociation has been proposed, taking into account the results obtained for related systems by independent methods: potentiometry, UV/VIS and EPR spectroscopies, X-ray diffraction analysis, and molecular mechanics calculations. ER -
LUBAL, Přemysl, Anne-Marie ALBRECHT-GARY, Silvie BLANC, Judite COSTA and Rita DELGADO. KINETIC AND MECHANISTIC STUDY OF DISSOCIATION OF COPPER(II) COMPLEX WITH 14-MEMBERED TETRAAZAMACROCYCLE LIGAND CONTAINING PYRIDINE AND N-CARBOXYMETHYL ARMS. \textit{Collection of Czechoslovak Chemical Communications}. Prague: Inst Org Chem Biochem Czech Acad Sci, 2008, vol.~73, No~2, p.~258-274, 16 pp. ISSN~0010-0765.
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