Thermodynamic and kinetic study of Copper(II) Complexes with
N-methylene(phenylphosphinic) Derivatives of Cyclen and Cyclam

J 2001

Thermodynamic and kinetic study of Copper(II) Complexes with N-methylene(phenylphosphinic) Derivatives of Cyclen and Cyclam

LUBAL, Přemysl, Mojmír KÝVALA, Petr HERMANN, Jana HOLUBOVÁ, Jan ROHOVEC et. al.

Basic information

Original name

Thermodynamic and kinetic study of Copper(II) Complexes with N-methylene(phenylphosphinic) Derivatives of Cyclen and Cyclam

Authors

LUBAL, Přemysl, Mojmír KÝVALA, Petr HERMANN, Jana HOLUBOVÁ, Jan ROHOVEC, Josef HAVEL and Ivan LUKEŠ

Edition

Polyhedron, Velká Británie, Elsevier Science Ltd. 2001, 0277-5387

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

Netherlands

Confidentiality degree

není předmětem státního či obchodního tajemství

Impact factor

Impact factor: 1.200

RIV identification code

RIV/00216224:14310/01:00002919

Organization unit

Faculty of Science

Keywords in English

polyazamacrocycles phosphinic acids; cyclen and cyclam derivatives; copper(II) complexes; potentiometry; kinetics; stability constants

Abstract

V originále

Equilibria of Cu(II) with newly synthetised ligands H4L1 and H4L2 were investigated by the glass electrode potentiometry at 25 degrees of Celsius and I = 0.1 M KNO3. A simple chemical model with metal:ligand molar ratio 1:1 was found in the systems. Presence of main species , CuL1 (log Beta = 20.37(4)) and CuL2 (log Beta = 17.19(2)) was also confirmed by MALDI-TOF/MS. The dissociation kinetics of the complexes was followed by spectrophotometry and mechanism of the dissociation was proposed. Activation parameters (activation enthalpy and entropy) of the dissociation were estimated. For Cu(II)-H4L1 system, the complex dissociation starts after protonization of phosphinic pendant arms and its mechasnism is similar to the decomplexation of [Cu(cyclen)]2+. The complex with H4L2 is kinetically much less stable and the proton transfer from phosphinic pendant arm to the azacycle plays a significant role in the reaction mechanism.

Links

GA203/97/0252, research and development project

Name: Makrocyklické azacykly obsahující fosfinovou skupinu. Syntéza a komplexotvorné vlastnosti

Investor: Czech Science Foundation, Macrocyclic azacycles containing phosphinic group.Synthesis and complexing properties

MSM 143100011, plan (intention)

Name: Struktura a vazebné poměry, vlastnosti a analýza syntetických a přírodních molekulových ansamblů

Investor: Ministry of Education, Youth and Sports of the CR, Structure and character of bonding, properties and analysis of synthetic and natural molecular ensembles

Citovat

LUBAL, Přemysl, Mojmír KÝVALA, Petr HERMANN, Jana HOLUBOVÁ, Jan ROHOVEC, Josef HAVEL and Ivan LUKEŠ. Thermodynamic and kinetic study of Copper(II) Complexes with N-methylene(phenylphosphinic) Derivatives of Cyclen and Cyclam. Polyhedron. Velká Británie: Elsevier Science Ltd., 2001, vol. 20, No 1, p. 47-55. ISSN 0277-5387.

@article{350672,
   author = {Lubal, Přemysl and Kývala, Mojmír and Hermann, Petr and Holubová, Jana and Rohovec, Jan and Havel, Josef and Lukeš, Ivan},
   article_location = {Velká Británie},
   article_number = {1},
   keywords = {polyazamacrocycles phosphinic acids; cyclen and cyclam derivatives; copper(II) complexes; potentiometry; kinetics; stability constants},
   language = {eng},
   issn = {0277-5387},
   journal = {Polyhedron},
   title = {Thermodynamic and kinetic study of Copper(II) Complexes with N-methylene(phenylphosphinic) Derivatives of Cyclen and Cyclam},
   volume = {20},
   year = {2001}
}

TY  - JOUR
ID  - 350672
AU  - Lubal, Přemysl - Kývala, Mojmír - Hermann, Petr - Holubová, Jana - Rohovec, Jan - Havel, Josef - Lukeš, Ivan
PY  - 2001
TI  - Thermodynamic and kinetic study of Copper(II) Complexes with N-methylene(phenylphosphinic) Derivatives of Cyclen and Cyclam
JF  - Polyhedron
VL  - 20
IS  - 1
SP  - 47
EP  - 47
PB  - Elsevier Science Ltd.
SN  - 02775387
KW  - polyazamacrocycles phosphinic acids
KW  - cyclen and cyclam derivatives
KW  - copper(II) complexes
KW  - potentiometry
KW  - kinetics
KW  - stability constants
N2  - Equilibria of Cu(II) with newly synthetised ligands H4L1 and H4L2 were investigated by the glass electrode potentiometry at 25 degrees of Celsius and I = 0.1 M KNO3. A simple chemical model with metal:ligand molar ratio 1:1 was found in the systems. Presence of main species , CuL1 (log Beta = 20.37(4)) and CuL2 (log Beta = 17.19(2)) was also confirmed by MALDI-TOF/MS. The dissociation kinetics of the complexes was followed by spectrophotometry and mechanism of the dissociation was proposed. Activation parameters (activation enthalpy and entropy) of the dissociation were estimated. For Cu(II)-H4L1 system, the complex dissociation starts after protonization of phosphinic pendant arms and its mechasnism is similar to the decomplexation of [Cu(cyclen)]2+. The complex with H4L2 is kinetically much less stable and the proton transfer from phosphinic pendant arm to the azacycle plays a significant role in the reaction mechanism.
ER  -

LUBAL, Přemysl, Mojmír KÝVALA, Petr HERMANN, Jana HOLUBOVÁ, Jan ROHOVEC, Josef HAVEL and Ivan LUKEŠ. Thermodynamic and kinetic study of Copper(II) Complexes with N-methylene(phenylphosphinic) Derivatives of Cyclen and Cyclam. \textit{Polyhedron}. Velká Británie: Elsevier Science Ltd., 2001, vol.~20, No~1, p.~47-55. ISSN~0277-5387.

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