Detailed Information on Publication Record
2013
Dissociation kinetics study of copper(II) complexes of DO3A, DOTA and its monosubstituted derivatives
VORÁČOVÁ, Ivona, Jakub VANĚK, Josef PASULKA, Zora STŘELCOVÁ, Přemysl LUBAL et. al.Basic information
Original name
Dissociation kinetics study of copper(II) complexes of DO3A, DOTA and its monosubstituted derivatives
Authors
VORÁČOVÁ, Ivona (203 Czech Republic), Jakub VANĚK (203 Czech Republic, belonging to the institution), Josef PASULKA (203 Czech Republic, belonging to the institution), Zora STŘELCOVÁ (203 Czech Republic, belonging to the institution), Přemysl LUBAL (203 Czech Republic, guarantor, belonging to the institution) and Petr HERMANN (203 Czech Republic)
Edition
Polyhedron, OXFORD, Elsevier Science Ltd. 2013, 0277-5387
Other information
Language
English
Type of outcome
Článek v odborném periodiku
Field of Study
10402 Inorganic and nuclear chemistry
Country of publisher
United Kingdom of Great Britain and Northern Ireland
Confidentiality degree
není předmětem státního či obchodního tajemství
References:
Impact factor
Impact factor: 2.047
RIV identification code
RIV/00216224:14740/13:00066398
Organization unit
Central European Institute of Technology
UT WoS
000322938100014
Keywords in English
Macrocyclic ligands; Cyclen derivatives; Phosphonate complexes; Phosphinate complexes; Pyridine-N-oxide complexes; Copper complexes; Dissociation kinetics; Rate constants; Radiopharmaceuticals
Tags
International impact, Reviewed
Změněno: 11/4/2014 00:45, Olga Křížová
Abstract
V originále
The kinetic inertness of copper(II) complexes with cyclen-based ligands having three (H(3)do3a) or four (H(4)dota) acetic acid arms and those with three acetic acid and one phosphonic (H(5)do3ap), phosphinic (H(5)do(3)ap(PrA) , H(4)do3ap(ABn)) acid or methylpyridine-N-oxide (H(3)do3a-pyNox) pendant arms has been studied. The proton-assisted decomplexation reaction was studied under a wide range of conditions to fully assess the parameters influencing the reaction (temperature range 25-60 degrees C, proton concentration range 0.05-5 M and presence of perchlorate or nitrate anions). The empirical rate law k(d,obs) = k(0) + k(H) x [H+], involving solvolytic and proton-assisted dissociation pathways, shows that the complexes can be divided into two groups according to their kinetic behavior. Complexes of ligands having only carboxylate pendant arms (H(3)do(3)a, H(4)dota) show higher kinetic inertness than those of ligands with mixed pendant arms (H(5)do(3)ap, H(5)do(3)ap(PrA), H(4)do3ap(ABn), H(3)do3a-pyNox). Linear Free Energy Relationship (LFER) analysis of the activation parameters (Delta H#, Delta S#) proves that the reaction mechanism is generally the same for all copper(II) complexes and is independent of the inert electrolyte. Rate constants representing both solvolytic and acid-assisted pathways roughly correlate with the basicity of the ring nitrogen atoms. The nitrate anion from the supporting electrolyte was shown to accelerate (by about 3-5 times) the decomplexation reaction when compared to the reaction in perchlorate-containing media; the nitrate anion seems to interact with the reaction intermediates, changing the activation parameters of both reaction pathways. This effect is somewhat suppressed in the complex of the ligand with a hydrophobic p-aminobenzyl substituent on the phosphorus atom, H(5)do3ap(ABn). In perchlorate media, complexes of the monophosphorus acid H(4)dota analogs are less kinetically inert.
Links
| ED1.1.00/02.0068, research and development project |
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| GA13-08336S, research and development project |
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| ME09065, research and development project |
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