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, 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.

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

• Original language: English
• Type of outcome: Article in a journal
• Field of Study: 10402 Inorganic and nuclear chemistry
• Country of publisher: Netherlands
• Confidentiality degree: is not subject to a state or trade secret
• 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
• Tags: copper(II) complexes, cyclen and cyclam derivatives, kinetics, polyazamacrocycles phosphinic acids, potentiometry, Stability Constants

Abstract

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