Phenolate-bridged zinc(II) complexes relevant to biological phosphoester cleavage

作者:Gruenwald Katrin R; Volpe Manuel; Moesch Zanetti Nadia C
来源:Journal of Coordination Chemistry, 2012, 65(11): 2008-2020.
DOI:10.1080/00958972.2012.688117

摘要

Three zinc complexes based on 2,6-bis(N-2-pyridylmethyl) formimidoyl-4-methylphenolate (HL) by employing Zn(ClO4)(2), Zn(CH3COO)(2), and ZnCl2 have been synthesized and investigated as functional models of phosphoesterases. The molecular structure of [{Zn2L(mu(3)-OH)(H2O)}(2)](ClO4)(4) (1) obtained by reacting zinc perchlorate with HL was determined by X-ray diffraction analysis, revealing a tetranuclear species with four zinc centers and two ligands. Two zinc ions are accommodated within the two compartments of each ligand and are bridged by an additional hydroxide leading to Zn-Zn distances of 3.1235(9) and 3.1268(9) angstrom, respectively. The hydroxide is involved in an additional bridge to the second LZn2 moiety forming a mu(3)-OH. A water molecule is coordinated to two of the four zinc ions. The occurrence of a hydroxide group and of a coordinated water is relevant to the structure found in the native enzyme. The hydrolysis of the phosphoester bis(p-nitrophenol) phosphate ester (BNPP) in a mixture of DMSO and water at 50 degrees C catalyzed by the three zinc compounds has been investigated. High hydrolytic activity was found for all three compounds but differed significantly depending on the nature of the counterion; the chloro derivative was found to be most active, while the perchlorate compound showed the least activity.

  • 出版日期2012