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. 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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Basic information
Original name KINETIC AND MECHANISTIC STUDY OF DISSOCIATION OF COPPER(II) COMPLEX WITH 14-MEMBERED TETRAAZAMACROCYCLE LIGAND CONTAINING PYRIDINE AND N-CARBOXYMETHYL ARMS
Name in Czech KINETICKÉ A MECHANISTICKÉ STUDIUM DISSOCIACE Cu(II) KOMPLEXU S 14-ČLENNÝM TETRAAZAMAKROCYKLICKÝM LIGANDEM OBSAHUJÍCÍ PYRIDINE A N-CARBOXYMETHYL FUNKČNÍ SKUPINY
Authors LUBAL, Přemysl (203 Czech Republic, guarantor), Anne-Marie ALBRECHT-GARY (250 France), Silvie BLANC (250 France), Judite COSTA (620 Portugal) and Rita DELGADO (620 Portugal).
Edition Collection of Czechoslovak Chemical Communications, Prague, Inst Org Chem Biochem Czech Acad Sci, 2008, 0010-0765.
Other information
Original language English
Type of outcome Article in a journal
Field of Study 10402 Inorganic and nuclear chemistry
Country of publisher Czech Republic
Confidentiality degree is not subject to a state or trade secret
Impact factor Impact factor: 0.784
RIV identification code RIV/00216224:14310/08:00033551
Organization unit Faculty of Science
UT WoS 000253884000009
Keywords in English Copper(II) complexes; Pendant acetate arms; Tetraaza-macrocyclic ligands; Aza-crown macrocycles; Pyridinylbackbone
Tags Aza-crown macrocycles, copper(II) complexes, Pendant acetate arms, Pyridinylbackbone, Tetraaza-macrocyclic ligands
Tags International impact, Reviewed
Changed by Changed by: prof. RNDr. Přemysl Lubal, Ph.D., učo 1271. Changed: 7/4/2010 17:37.
Abstract
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.
Abstract (in Czech)
Kinetika kysele katalyzované disociace Cu(II) komplexu s 7-methyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene-3,11-diacetic acid (ac2Me[14]pyN4) při [H+] = 0.05-0.25 M, I = 0.25 M (Na, H)ClO4, and T = 298.16 K byla studována pomocí konvenční a "stopped-flow" UV/VIS spektroskopie. Bylo stanoveno, že následná složená reakce se skládá ze 3 kroků. Velmi rychlé první a druhý krok je charakterizován rychlostními konstantami k1 = 70 +/- 10 a k2 = 0.23 +/- 0.01 M-1 s-1 a obě závisí na koncentraci protonů. Poslední třetí krok je velmi pomalý, k3 = (1.08 +/- 0.03) * 10-3 s-1, a nezávisí na koncentraci protonů. Tento rychlost-určující krok zahrnuje isomerizační proces, který je následován rychlým krokem uvolnění Cu(II) iontu z dutiny macrocyklu. Byl navržen reakční mechanismus disociace komplexu, jestliže bereme do úvahy výsledky zjištěné pomocí jiných exp. metod. : potenciometrie, UV/VIS a EPR spektroskopie, RTG strukturní analýza a výpočty založené na molekulové mechanice.
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