Electroreductive Decomplexation and Isomerism of Copper(II) Complexes with Cyclam Ligands for Medical Use

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00584313" target="_blank" >RIV/61388955:_____/24:00584313 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/24:10480937

Výsledek na webu

<a href="https://hdl.handle.net/11104/0352244" target="_blank" >https://hdl.handle.net/11104/0352244</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/celc.202300833" target="_blank" >10.1002/celc.202300833</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electroreductive Decomplexation and Isomerism of Copper(II) Complexes with Cyclam Ligands for Medical Use

Popis výsledku v původním jazyce

Detailed electrochemical study of copper(II) complexes of cyclam bearing two phosphonate (TE2P), phenolate (TE2PhOH) or carboxylate (TE2A) pendant arms (together with one cross-bridged-cyclam derivative cb-TE2A) was performed using cyclic voltammetry (CV) and polarography. The electrochemical-heterogeneous measurements were accompanied by UV-vis spectra describing the situation in homogeneous phase. Reduction of complexes on mercury electrode in buffered aqueous solutions (pH 2–12) occurs generally as a two-electron process of reductive decomposition. The formed Cu-amalgam can be (e. g. during the anodic scan of CV) reoxidized to Cu(II) cation which undergoes re-complexation resulting in the original complex. This process of a square diagram is manifold repeatable. The results also showed presence of several isomers differing in mutual orientation of substituents on cyclam nitrogen atoms. The primary “kinetic”, pentacoordinated isomers are irreversibly transformed to the stable, hexacoordinated “thermodynamic” ones upon heating. The development of isomerization process was followed electrochemically. The cross-bridged cb-TE2A derivative forms only one isomer which does not change even after heating. The higher stability of the complex manifests itself at pH>8 when the complex is reversibly reduced in one-electron step, formally CuII/CuI, without decomposition.

Název v anglickém jazyce

Electroreductive Decomplexation and Isomerism of Copper(II) Complexes with Cyclam Ligands for Medical Use

Popis výsledku anglicky

Detailed electrochemical study of copper(II) complexes of cyclam bearing two phosphonate (TE2P), phenolate (TE2PhOH) or carboxylate (TE2A) pendant arms (together with one cross-bridged-cyclam derivative cb-TE2A) was performed using cyclic voltammetry (CV) and polarography. The electrochemical-heterogeneous measurements were accompanied by UV-vis spectra describing the situation in homogeneous phase. Reduction of complexes on mercury electrode in buffered aqueous solutions (pH 2–12) occurs generally as a two-electron process of reductive decomposition. The formed Cu-amalgam can be (e. g. during the anodic scan of CV) reoxidized to Cu(II) cation which undergoes re-complexation resulting in the original complex. This process of a square diagram is manifold repeatable. The results also showed presence of several isomers differing in mutual orientation of substituents on cyclam nitrogen atoms. The primary “kinetic”, pentacoordinated isomers are irreversibly transformed to the stable, hexacoordinated “thermodynamic” ones upon heating. The development of isomerization process was followed electrochemically. The cross-bridged cb-TE2A derivative forms only one isomer which does not change even after heating. The higher stability of the complex manifests itself at pH>8 when the complex is reversibly reduced in one-electron step, formally CuII/CuI, without decomposition.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

ChemElectroChem

ISSN

2196-0216

e-ISSN

2196-0216

Svazek periodika

11

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

e202300833

Kód UT WoS článku

001180914400001

EID výsledku v databázi Scopus

2-s2.0-85186914106