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 (203 Česká republika), M. KÝVALA (203 Česká republika), P. HERMANN (203 Česká republika), J. HOLUBOVÁ (203 Česká republika), J. ROHOVEC (203 Česká republika), Josef HAVEL (203 Česká republika) a Ivan LUKEŠ (203 Česká republika, garant)

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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