Jump to main content
Jump to site search

Issue 1, 2006
Previous Article Next Article

Catalytic alcohol oxidation by an unsymmetrical 5-coordinate copper complex: electronic structure and mechanism

Author affiliations

Abstract

Density functional theory reveals the detailed mechanism of alcohol oxidation by a model copper complex, CuIIL, L = cis-1-(3′,5′-dimethoxy-benzylideneamino)-3,5-[2-hydroxy-(3′,5′-di-tert-butyl)benzylideneimino]cyclohexane. Despite the obvious structural and functional parallels between the title compound and the enzyme galactose oxidase, the details of the catalytic pathway are fundamentally different. In the enzyme, coordination of the substrate produces an active form containing a CuII centre and a tyrosyl radical, the latter being responsible for the abstraction of hydrogen from the substrate. In the model system, in marked contrast, the active form contains a CuII centre, but the ligand radical character is localised on the substrate (alcoholate) oxygen, rather than the phenolate ligand. The result is a significantly higher barrier to hydrogen-atom abstraction compared to the enzyme itself. The origin of these significant differences is traced to the rigid nature of the pentadentate ligand, which resists changes in coordination number during the catalytic cycle.

Graphical abstract: Catalytic alcohol oxidation by an unsymmetrical 5-coordinate copper complex: electronic structure and mechanism

Back to tab navigation

Supplementary files

Publication details

The article was received on 30 Aug 2005, accepted on 25 Oct 2005 and first published on 15 Nov 2005


Article type: Paper
DOI: 10.1039/B512298H
Citation: Dalton Trans., 2006,0, 159-167
  •   Request permissions

    Catalytic alcohol oxidation by an unsymmetrical 5-coordinate copper complex: electronic structure and mechanism

    E. Zueva, P. H. Walton and J. E. McGrady, Dalton Trans., 2006, 0, 159
    DOI: 10.1039/B512298H

Search articles by author

Spotlight

Advertisements