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.

Základní údaje

Originální název

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

Autoři

LUBAL, Přemysl; M. KÝVALA; P. HERMANN; J. HOLUBOVÁ; J. ROHOVEC; Josef HAVEL a Ivan LUKEŠ

Vydání

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

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10406 Analytical chemistry

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Impakt faktor

Impact factor: 1.200

Kód RIV

RIV/00216224:14310/01:00008545

Organizační jednotka

Přírodovědecká fakulta

UT WoS

000167008300004

Klíčová slova anglicky

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

Štítky

copper(II) complexes, cyclen and cyclam derivatives, kinetics, phosphinic acids, Polyazamacrocycles, potenciometry, Stability Constants

Změněno: 31. 5. 2004 17:15, prof. RNDr. Přemysl Lubal, Ph.D.

Anotace

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.

Návaznosti

GA203/97/0252, projekt VaV

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

Investor: Grantová agentura ČR, Makrocyklické azacykly obsahující fosfinovou skupinu. Syntéza a komplexotvorné vlastnosti

MSM 143100011, záměr

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

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Struktura a vazebné poměry, vlastnosti a analýza syntetických a přírodních molekulových ansamblů

Citovat

LUBAL, Přemysl; M. KÝVALA; P. HERMANN; J. HOLUBOVÁ; J. ROHOVEC; Josef HAVEL a 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, roč. 20, 1-2, s. 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 a 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, roč.~20, 1-2, s.~47-55. ISSN~0277-5387.

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