Thermodynamic and kinetic study of copper(II) complexes with
N-methylene(phenylphosphinic acid) derivatives of cyclen and
cyclam

J 2001

Thermodynamic and kinetic study of copper(II) complexes with N-methylene(phenylphosphinic acid) derivatives of cyclen and cyclam

LUBAL, Přemysl, M. KÝVALA, P. HERMANN, J. HOLUBOVÁ, J. ROHOVEC et. al.

Basic information

Original name

Thermodynamic and kinetic study of copper(II) complexes with N-methylene(phenylphosphinic acid) derivatives of cyclen and cyclam

Authors

LUBAL, Přemysl (203 Czech Republic), M. KÝVALA (203 Czech Republic), P. HERMANN (203 Czech Republic), J. HOLUBOVÁ (203 Czech Republic), J. ROHOVEC (203 Czech Republic), Josef HAVEL (203 Czech Republic) and Ivan LUKEŠ (203 Czech Republic, guarantor)

Edition

Polyhedron, Oxford, Pergamon-Elsevier Science, 2001, 0277-5387

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10406 Analytical chemistry

Country of publisher

United Kingdom of Great Britain and Northern Ireland

Confidentiality degree

není předmětem státního či obchodního tajemství

Impact factor

Impact factor: 1.200

RIV identification code

RIV/00216224:14310/01:00008545

Organization unit

Faculty of Science

UT WoS

000167008300004

Keywords in English

Polyazamacrocycles; phosphinic acids; cyclen and cyclam derivatives; copper(II) complexes; potenciometry; kinetics; stability constants

Abstract

V originále

Equilibria in the Cu2+-H4L1 and Cu2+-H4L2 systems, where H4L1 is 1,4,7,10-tetraaza-cyclododecane-1,4,7,10-tetrayl-tramethylene-tetrakis(phenylphosphinic acid) and H4L2 is 1,4,8,11-tetraaza-cyclotetradecane-1,4,8,11-tetrayl-tetramethylene-tetrakis(phenylphosphinic acid), were investigated by glass electrode potentiometry at 25 degreesC (I = 0.1 mol dm(-3) KNO3). A simple chemical model with the metal:ligand molar ratio 1:1 was found in the systems. The presence of main species, [CuL1](2-)(log beta = 20.37(4)) and [CuL2](2-) (log beta = 17.19(2)), was also confirmed by MALDI-TOF/MS. The dissociation kinetics of the complexes was followed by spectrophotometry and a mechanism of the dissociation was proposed. Activation parameters (activation enthalpy and entropy) of the dissociation were estimated. For the Cu2+ -H4L1 system, the complex dissociation starts after protonation of the phosphinic pendant arms and its mechanism is similar to the decomplexation of [Cu(cyclen)](2+). The Cu2+ complex with H4L2 is kinetically much less stable. The proton transfer from the phosphinic pendant arm to the azacycle plays a significant role in the reaction mechanism of both the complexes.

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, M. KÝVALA, P. HERMANN, J. HOLUBOVÁ, J. ROHOVEC, Josef HAVEL and Ivan LUKEŠ. Thermodynamic and kinetic study of copper(II) complexes with N-methylene(phenylphosphinic acid) derivatives of cyclen and cyclam. Polyhedron. Oxford: Pergamon-Elsevier Science, 2001, vol. 20, 1-2, p. 47-55. ISSN 0277-5387.

@article{390689,
   author = {Lubal, Přemysl and Kývala, M. and Hermann, P. and Holubová, J. and Rohovec, J. and Havel, Josef and Lukeš, Ivan},
   article_location = {Oxford},
   article_number = {1-2},
   keywords = {Polyazamacrocycles; phosphinic acids; cyclen and cyclam derivatives; copper(II) complexes; potenciometry; kinetics; stability constants},
   language = {eng},
   issn = {0277-5387},
   journal = {Polyhedron},
   title = {Thermodynamic and kinetic study of copper(II) complexes with N-methylene(phenylphosphinic acid) derivatives of cyclen and cyclam},
   volume = {20},
   year = {2001}
}

TY  - JOUR
ID  - 390689
AU  - Lubal, Přemysl - Kývala, M. - Hermann, P. - Holubová, J. - Rohovec, J. - Havel, Josef - Lukeš, Ivan
PY  - 2001
TI  - Thermodynamic and kinetic study of copper(II) complexes with N-methylene(phenylphosphinic acid) derivatives of cyclen and cyclam
JF  - Polyhedron
VL  - 20
IS  - 1-2
SP  - 47-55
EP  - 47-55
PB  - Pergamon-Elsevier Science
SN  - 02775387
KW  - Polyazamacrocycles
KW  - phosphinic acids
KW  - cyclen and cyclam derivatives
KW  - copper(II) complexes
KW  - potenciometry
KW  - kinetics
KW  - stability constants
N2  - Equilibria in the Cu2+-H4L1 and Cu2+-H4L2 systems, where H4L1 is 1,4,7,10-tetraaza-cyclododecane-1,4,7,10-tetrayl-tramethylene-tetrakis(phenylphosphinic acid) and H4L2 is 1,4,8,11-tetraaza-cyclotetradecane-1,4,8,11-tetrayl-tetramethylene-tetrakis(phenylphosphinic acid), were investigated by glass electrode potentiometry at 25 degreesC (I = 0.1 mol dm(-3) KNO3). A simple chemical model with the metal:ligand molar ratio 1:1 was found in the systems. The presence of main species, [CuL1](2-)(log beta = 20.37(4)) and [CuL2](2-) (log beta = 17.19(2)), was also confirmed by MALDI-TOF/MS. The dissociation kinetics of the complexes was followed by spectrophotometry and a mechanism of the dissociation was proposed. Activation parameters (activation enthalpy and entropy) of the dissociation were estimated. For the Cu2+ -H4L1 system, the complex dissociation starts after protonation of the phosphinic pendant arms and its mechanism is similar to the decomplexation of [Cu(cyclen)](2+). The Cu2+ complex with H4L2 is kinetically much less stable. The proton transfer from the phosphinic pendant arm to the azacycle plays a significant role in the reaction mechanism of both the complexes.
ER  -

LUBAL, Přemysl, M. KÝVALA, P. HERMANN, J. HOLUBOVÁ, J. ROHOVEC, Josef HAVEL and Ivan LUKEŠ. Thermodynamic and kinetic study of copper(II) complexes with N-methylene(phenylphosphinic acid) derivatives of cyclen and cyclam. \textit{Polyhedron}. Oxford: Pergamon-Elsevier Science, 2001, vol.~20, 1-2, p.~47-55. ISSN~0277-5387.

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