TY - JOUR
T1 - Equilibria and formation kinetics of some cyclen derivative complexes of lanthanides
AU - Szilágyi, Erika
AU - Tóth, Éva
AU - Kovács, Zoltán
AU - Platzek, Johannes
AU - Radüchel, Bernd
AU - Brücher, Ernö
N1 - Funding Information:
This work was supported by the Hungarian Scientific Research Foundation (OTKA T 025 462).
PY - 2000/2/15
Y1 - 2000/2/15
N2 - The kinetics of the formation reactions between the lanthanide(III) ions Ce3+, Eu3+ and Yb3+ and four cyclen derivative ligands, DO3A-B, DO3A-ME, DO2A and DO2A-2B, were studied by spectrophotometry and a stopped-flow method at 25°C in 1.0 M KCl solutions. The reactions were found to be of first order, which was interpreted in terms of the formation of a diprotonated intermediate, Ln(H2L)+. The formation of products occurs via deprotonation and rearrangement of the intermediate, characterised by the rate constant, k(r). The rate law obtained, k(r) = k(OH)[OH-], is similar to those obtained for the formation reactions of DOTA and DOTA derivative complexes. The rate constants, k(OH), decrease with decrease in the number of charged carboxylate functional groups in the ligands; the lowest rates were found for the formation of the DO2A complexes. The formation rates increase significantly from Ce3+ to Yb3+. The direct proportionality between the formation rates and [H+]- was interpreted by assuming the equilibrium formation of a monoprotonated intermediate, Ln(HL), which undergoes deprotonation in a slow, rate-determining step. The validity of general base catalysis was detected in the formation reactions, which supports the assumption of the rate-controlling role of deprotonation of the monoprotonated intermediate. The protonation constants of the ligands DO3A-ME and DO2A-2B and the stability constants of their complexes were also determined. The ligand DO2A forms the usual complexes Ln(DO2A)+ and the unusual species Ln(DO2A)2-. In the complexes Ln(DO2A)2-, the two ligands exhibit different coordination modes which were demonstrated by 1H NMR spectroscopy. (C) 2000 Elsevier Science S.A.
AB - The kinetics of the formation reactions between the lanthanide(III) ions Ce3+, Eu3+ and Yb3+ and four cyclen derivative ligands, DO3A-B, DO3A-ME, DO2A and DO2A-2B, were studied by spectrophotometry and a stopped-flow method at 25°C in 1.0 M KCl solutions. The reactions were found to be of first order, which was interpreted in terms of the formation of a diprotonated intermediate, Ln(H2L)+. The formation of products occurs via deprotonation and rearrangement of the intermediate, characterised by the rate constant, k(r). The rate law obtained, k(r) = k(OH)[OH-], is similar to those obtained for the formation reactions of DOTA and DOTA derivative complexes. The rate constants, k(OH), decrease with decrease in the number of charged carboxylate functional groups in the ligands; the lowest rates were found for the formation of the DO2A complexes. The formation rates increase significantly from Ce3+ to Yb3+. The direct proportionality between the formation rates and [H+]- was interpreted by assuming the equilibrium formation of a monoprotonated intermediate, Ln(HL), which undergoes deprotonation in a slow, rate-determining step. The validity of general base catalysis was detected in the formation reactions, which supports the assumption of the rate-controlling role of deprotonation of the monoprotonated intermediate. The protonation constants of the ligands DO3A-ME and DO2A-2B and the stability constants of their complexes were also determined. The ligand DO2A forms the usual complexes Ln(DO2A)+ and the unusual species Ln(DO2A)2-. In the complexes Ln(DO2A)2-, the two ligands exhibit different coordination modes which were demonstrated by 1H NMR spectroscopy. (C) 2000 Elsevier Science S.A.
KW - Cyclen complexes
KW - Lanthanide complexes
KW - Stability constants
UR - http://www.scopus.com/inward/record.url?scp=0034651448&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0034651448&partnerID=8YFLogxK
U2 - 10.1016/S0020-1693(99)00467-3
DO - 10.1016/S0020-1693(99)00467-3
M3 - Article
AN - SCOPUS:0034651448
SN - 0020-1693
VL - 298
SP - 226
EP - 234
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 2
ER -