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

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F16%3A10326123" target="_blank" >RIV/00216208:11310/16:10326123 - isvavai.cz</a>

Alternative codes found

RIV/00216224:14310/16:00088303

Result on the web

<a href="http://dx.doi.org/10.1039/c6dt01127f" target="_blank" >http://dx.doi.org/10.1039/c6dt01127f</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c6dt01127f" target="_blank" >10.1039/c6dt01127f</a>

Result language

angličtina

Original language name

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

Original language description

The kinetic properties of Cu(II) complexes of H(4)dota and its analogues with one (H(5)do3ap), two (trans-H(6)do2a2p), three (H(7)doa3p) and four (H(8)dotp) phosphonic acid pendant arms were investigated. The formation of a Cu(II) complex with H(4)dota, trans-H(6)do2a2p and H(8)dotp at a slightly acidic pH is faster for the phosphonic acid derivatives than for H(4)dota, but with no simple dependence on the number of -CH2PO3H2 substituents (trans-H(6)do2a2p > H(8)dotp > H(4)dota; pH 4-6). Relative differences in the reactivity among the differently protonated species (HnLx-) 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 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 of Cu(II) complexes follows the order: H(4)dota > H(5)do3ap > trans-H(6)do2a2p > H(7)doa3p > H(8)dotp. Analogous data were obtained for trans-H(2)do2a and its Cu(II) complex kinetic inertness is similar to that of the H(4)dota complex. As it was considered that the published thermodynamics data on the Cu(II)-H(8)dotp 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 (H(6)doa3p)(-) anion in the solid state was determined. These experimental data demonstrate that the substitution of acetic acid pendant arms by methylphosphonic acid ones in H(4)dota-like ligands increases the rate of complexation but significantly decreases the kinetic inertness of the Cu(II) complexes.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CA - Inorganic chemistry

OECD FORD branch

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Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2016

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Dalton Transactions

ISSN

1477-9226

e-ISSN

—

Volume of the periodical

45

Issue of the periodical within the volume

32

Country of publishing house

GB - UNITED KINGDOM

Number of pages

11

Pages from-to

12723-12733

UT code for WoS article

000381478500017

EID of the result in the Scopus database

2-s2.0-84982094879