Formation and decomplexation kinetics of copper(II) complexes
with cyclen derivatives having mixed carboxylate and
phosphonate pendant arms

J 2016

Formation and decomplexation kinetics of copper(II) complexes with cyclen derivatives having mixed carboxylate and phosphonate pendant arms

ŠEVČÍK, Radek, Jakub VANĚK, Romana MICHALICOVÁ, Přemysl LUBAL, Petr HERMANN et. al.

Basic information

Original name

Formation and decomplexation kinetics of copper(II) complexes with cyclen derivatives having mixed carboxylate and phosphonate pendant arms

Authors

ŠEVČÍK, Radek (203 Czech Republic, belonging to the institution), Jakub VANĚK (203 Czech Republic, belonging to the institution), Romana MICHALICOVÁ (203 Czech Republic, belonging to the institution), Přemysl LUBAL (203 Czech Republic, guarantor, belonging to the institution), Petr HERMANN (203 Czech Republic), I.C. SANTOS (620 Portugal), I. SANTOS (620 Portugal) and M.P.C CAMPELLO (620 Portugal)

Edition

Dalton Transactions, Royal Society of Chemistry, 2016, 1477-9226

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

Impact factor

Impact factor: 4.029

RIV identification code

RIV/00216224:14310/16:00088303

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1039/c6dt01127f

UT WoS

000381478500017

Keywords in English

POSITRON EMISSION TOMOGRAPHY; METAL COMPLEXES; DISSOCIATION KINETICS; COPPER64 RADIOPHARMACEUTICALS; MEDICAL APPLICATIONS

Abstract

V originále

The kinetic properties of Cu(II) complexes of H4dota and its analogues with one (H5do3ap), two in the 1,7-position (trans-H6do2a2p), three (H7doa3p) and four (H8dotp) phosphonic acid pendant arms were investigated. Relative differences in the reactivity among the differently protonated species of the same ligand are successively decreased with the more phosphonic acid groups in the ligand. The faster complexation is probably caused by the higher ability of phosphonates to bind the metal ion and/or to assist in the transfer of protons from the ring amine groups to the bulk water. The acid-assisted decomplexation kinetics of the complexes was followed in highly acidic solutions ([H+] = 0.01-5 M) and at different temperatures (15-70 degrees C) to determine the activation parameters of the reaction. The kinetic inertness of the Cu(II) complexes follows the order: H4dota; H5do3ap; trans-H6do2a2p; H7doa3p; H8dotp. To obtain information on the influence of additional pendant arms, analogous data were obtained for trans-H2do2a. The ligand is less reactive than H4dota, but the kinetic inertness of its Cu(II) complex is similar to that of the H4dota complex. As it was considered that the published thermodynamics data on the Cu(II)-H8dotp system are probably incorrect, the system was re-investigated. It showed a very high stability for the [Cu(dotp)](6-) species and the easy formation of several Cu2L species in the presence of an excess of the metal ion. Also, the structure of the (H6doa3p)- anion in the solid state was determined. These experimental data demonstrate that the substitution of acetic acid pendant arms by methylphosphonic acid ones in H4dota-like ligands significantly decreases the kinetic inertness of the Cu(II) complexes.

Links

GA13-08336S, research and development project

Name: Hybridní materiály založené na makrocyklických ligandech pro využití v medicíně

Investor: Czech Science Foundation

LQ1601, research and development project

Name: CEITEC 2020 (Acronym: CEITEC2020)

Investor: Ministry of Education, Youth and Sports of the CR

MUNI/A/1500/2015, interní kód MU

Name: Vývoj metod a instrumentace pro analýzu biologicky významných látek 2016

Investor: Masaryk University, Category A

Citovat

ŠEVČÍK, Radek, Jakub VANĚK, Romana MICHALICOVÁ, Přemysl LUBAL, Petr HERMANN, I.C. SANTOS, I. SANTOS and M.P.C CAMPELLO. Formation and decomplexation kinetics of copper(II) complexes with cyclen derivatives having mixed carboxylate and phosphonate pendant arms. Dalton Transactions. Royal Society of Chemistry, 2016, vol. 45, No 32, p. 12723-12733. ISSN 1477-9226. Available from: https://dx.doi.org/10.1039/c6dt01127f.

@article{1359167,
   author = {Ševčík, Radek and Vaněk, Jakub and Michalicová, Romana and Lubal, Přemysl and Hermann, Petr and Santos, I.C. and Santos, I. and Campello, M.P.C},
   article_number = {32},
   doi = {http://dx.doi.org/10.1039/c6dt01127f},
   keywords = {POSITRON EMISSION TOMOGRAPHY; METAL COMPLEXES; DISSOCIATION KINETICS; COPPER64 RADIOPHARMACEUTICALS; MEDICAL APPLICATIONS},
   language = {eng},
   issn = {1477-9226},
   journal = {Dalton Transactions},
   title = {Formation and decomplexation kinetics of copper(II) complexes with cyclen derivatives having mixed carboxylate and phosphonate pendant arms},
   volume = {45},
   year = {2016}
}

TY  - JOUR
ID  - 1359167
AU  - Ševčík, Radek - Vaněk, Jakub - Michalicová, Romana - Lubal, Přemysl - Hermann, Petr - Santos, I.C. - Santos, I. - Campello, M.P.C
PY  - 2016
TI  - Formation and decomplexation kinetics of copper(II) complexes with cyclen derivatives having mixed carboxylate and phosphonate pendant arms
JF  - Dalton Transactions
VL  - 45
IS  - 32
SP  - 12723-12733
EP  - 12723-12733
PB  - Royal Society of Chemistry
SN  - 14779226
KW  - POSITRON EMISSION TOMOGRAPHY
KW  - METAL COMPLEXES
KW  - DISSOCIATION KINETICS
KW  - COPPER64 RADIOPHARMACEUTICALS
KW  - MEDICAL APPLICATIONS
N2  - The kinetic properties of Cu(II) complexes of H4dota and its analogues with one (H5do3ap), two in the 1,7-position (trans-H6do2a2p), three (H7doa3p) and four (H8dotp) phosphonic acid pendant arms were investigated. Relative differences in the reactivity among the differently protonated species of the same ligand are successively decreased with the more phosphonic acid groups in the ligand. The faster complexation is probably caused by the higher ability of phosphonates to bind the metal ion and/or to assist in the transfer of protons from the ring amine groups to the bulk water. The acid-assisted decomplexation kinetics of the complexes was followed in highly acidic solutions ([H+] = 0.01-5 M) and at different temperatures (15-70 degrees C) to determine the activation parameters of the reaction. The kinetic inertness of the Cu(II) complexes follows the order: H4dota; H5do3ap; trans-H6do2a2p; H7doa3p; H8dotp. To obtain information on the influence of additional pendant arms, analogous data were obtained for trans-H2do2a. The ligand is less reactive than H4dota, but the kinetic inertness of its Cu(II) complex is similar to that of the H4dota complex. As it was considered that the published thermodynamics data on the Cu(II)-H8dotp system are probably incorrect, the system was re-investigated. It showed a very high stability for the [Cu(dotp)](6-) species and the easy formation of several Cu2L species in the presence of an excess of the metal ion. Also, the structure of the (H6doa3p)- anion in the solid state was determined. These experimental data demonstrate that the substitution of acetic acid pendant arms by methylphosphonic acid ones in H4dota-like ligands significantly decreases the kinetic inertness of the Cu(II) complexes.
ER  -

ŠEVČÍK, Radek, Jakub VANĚK, Romana MICHALICOVÁ, Přemysl LUBAL, Petr HERMANN, I.C. SANTOS, I. SANTOS and M.P.C CAMPELLO. Formation and decomplexation kinetics of copper(II) complexes with cyclen derivatives having mixed carboxylate and phosphonate pendant arms. \textit{Dalton Transactions}. Royal Society of Chemistry, 2016, vol.~45, No~32, p.~12723-12733. ISSN~1477-9226. Available from: https://dx.doi.org/10.1039/c6dt01127f.

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