Jump to main content
Jump to site search

Issue 1, 2006
Previous Article Next Article

Thioester hydrolysis reactivity of zinc hydroxide complexes: investigating reactivity relevant to glyoxalase II enzymes

Author affiliations

Abstract

A recently reported binuclear zinc hydroxide complex [(L1Zn2)(µ-OH)](ClO4)2 (1, L1 = 2,6-bis[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenolate monoanion) containing a single bridging hydroxide was examined for thioester hydrolysis reactivity. Treatment of 1 with hydroxyphenylthioacetic acid S-methyl ester in dry CD3CN results in no reaction after ∼65 h at 45(1) °C. Binuclear zinc hydroxide complexes of the N-methyl-N-((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine (L2) and N-methyl-N-((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)ethyl)amine (L3) chelate ligands were prepared by treatment of each ligand with molar equivalent amounts of Zn(ClO4)2·6H2O and KOH in methanol. These complexes, [(L2Zn)2(µ-OH)2](ClO4)2 (2) and [(L3Zn)2(µ-OH)2](ClO4)2 (3), which have been structurally characterized by X-ray crystallography, behave as 1 : 1 electrolytes in acetonitrile, indicating that the binuclear cations dissociate into monomeric zinc hydroxide species in solution. Treatment of 2 or 3 with one equivalent of hydroxyphenylthioacetic acid S-methyl ester per zinc center in acetonitrile results in the formation of a zinc α-hydroxycarboxylate complex, [(L2)Zn(O2CCH(OH)Ph)]ClO4·1.5H2O (4) or [(L3)Zn(O2CCH(OH)Ph)]ClO4·1.5H2O (5), and CH3SH. These reactions, to our knowledge, are the first reported examples of thioester hydrolysis mediated by zinc hydroxide complexes. The results of this study suggest that a terminal Zn–OH moiety may be required for hydrolysis reactivity with a thioester substrate.

Graphical abstract: Thioester hydrolysis reactivity of zinc hydroxide complexes: investigating reactivity relevant to glyoxalase II enzymes

Back to tab navigation

Supplementary files

Publication details

The article was received on 05 Sep 2005, accepted on 17 Oct 2005 and first published on 23 Nov 2005


Article type: Paper
DOI: 10.1039/B512515D
Citation: Dalton Trans., 2006,0, 183-192
  •   Request permissions

    Thioester hydrolysis reactivity of zinc hydroxide complexes: investigating reactivity relevant to glyoxalase II enzymes

    L. M. Berreau, A. Saha and A. M. Arif, Dalton Trans., 2006, 0, 183
    DOI: 10.1039/B512515D

Search articles by author

Spotlight

Advertisements