Characteristic mechanisms of the homogeneous and heterogeneous oxidation of aromatic amines with transition metal-oxalate complexes

A. B. Zaki, M. Y. El-Sheikh, J. Evans, S. A. El-Safty

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

The oxidation-reduction reactions of aromatic amines {o-aminophenol (o-AP), o-phenylenediamine (o-PDA) and p-phenylenediamine (p-PDA)} with Co(III)-, Mn(III)-, and Cu(II)-oxalate complexes have been investigated in homogeneous and heterogeneous systems. The kinetics of the redox reaction of both systems have been studied spectrophotometrically. The redox products were identified and characterised by diffuse reflectance spectroscopy (DRS), and mass spectrometry. The redox reactions follow first-order kinetics with respect to each of the reactants and first order in [amines] in homogeneous and heterogeneous (supported complexes on Amberlite IRA 904 anion-exchange resin) phases, respectively. However, the specific oxidation rate of the amines is found to follow the order, p-PDA > o-AP > o-PDA. The effect of the oxalate anion on the reaction rate of both systems was examined. There is a significant difference in the behaviour of the oxidation of o-AP and o-, p-PDA with all the metal complexes in both systems. Moreover, the oxidation of o-AP and o-, p-PDA appears to follow the outer- and inner-sphere mechanistic classification, respectively. (C) 2000 Elsevier Science Ltd.

Original languageEnglish
Pages (from-to)1317-1328
Number of pages12
JournalPolyhedron
Volume19
Issue number11
DOIs
Publication statusPublished - 2000 Jun 15
Externally publishedYes

Fingerprint

Oxalates
Redox reactions
Coordination Complexes
oxalates
Metal complexes
Oxidation-Reduction
Amines
Transition metals
amines
transition metals
Oxidation
oxidation
Negative ions
Amberlite (trademark)
oxidation-reduction reactions
anions
Kinetics
kinetics
Anion Exchange Resins
resins

Keywords

  • Amberlite anion-exchange resin
  • Aromatic amines
  • Homogeneous and heterogeneous
  • Metal-oxalate complexes
  • Oxalate anions
  • Oxidation

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Characteristic mechanisms of the homogeneous and heterogeneous oxidation of aromatic amines with transition metal-oxalate complexes. / Zaki, A. B.; El-Sheikh, M. Y.; Evans, J.; El-Safty, S. A.

In: Polyhedron, Vol. 19, No. 11, 15.06.2000, p. 1317-1328.

Research output: Contribution to journalArticle

Zaki, A. B. ; El-Sheikh, M. Y. ; Evans, J. ; El-Safty, S. A. / Characteristic mechanisms of the homogeneous and heterogeneous oxidation of aromatic amines with transition metal-oxalate complexes. In: Polyhedron. 2000 ; Vol. 19, No. 11. pp. 1317-1328.
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