Asymmetric zinc(II) complexes as functional and structural models for phosphoesterases.

نویسندگان

  • Lena J Daumann
  • Laurène Marty
  • Gerhard Schenk
  • Lawrence R Gahan
چکیده

We report two asymmetric ligands for the generation of structural and functional dinuclear metal complexes as phosphoesterase mimics. Two zinc(II) complexes, [Zn2(CH3L4)(CH3CO2)2](+) (CH3HL4 = 2-(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-methyl-6-(((pyridin-2-ylmethyl)amino)methyl)phenol) and [Zn2(CH3L5)(CH3CO2)2](+) (CH3HL5 = 2-(((2-methoxyethyl)(pyridine-2-ylmethyl)amino)methyl)-4-methyl-6-(((pyridin-2-ylmethyl)(4-vinylbenzyl)amino)methyl)phenol) were synthesized and characterized by X-ray crystallography. The structures showed that the ligands enforce a mixed 6,5-coordinate environment in the solid state. (1)H-, (13)C- and (31)P-NMR, mass spectrometry and infrared spectroscopy were used to further characterize the compounds in the solid state and in solution. The zinc(II) complexes hydrolyzed the organophosphate substrate bis-(2,4-dinitrophenol)phosphate (BDNPP), the nucleophile proposed to be a terminal water molecule (pK(a) 7.2). The ligand CH3HL4 was immobilised on Merrifield resin and its zinc(II) complex generated. Infrared spectroscopy, microanalysis and XPS measurements confirmed successful immobilisation, with a catalyst loading of ~1.45 mmol g(-1) resin. The resin bound complex was active towards BDNPP and displayed similar pH dependence to the complex in solution.

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عنوان ژورنال:
  • Dalton transactions

دوره 42 26  شماره 

صفحات  -

تاریخ انتشار 2013