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Rapid hydrolysis of phosphate monoesters by zirconium(IV) complexes in neutral solution

Erxleben, Andrea
; 
Coleman, Fergal
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Publication Date
2012
Keywords
Zirconium, Catalysis, Phosphate ester hydrolysis, P-nitrophenyl phosphate, Reactivity, Diesters, Model, Phosphorothioate
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Coleman, F,Erxleben, A (2012) 'Rapid hydrolysis of phosphate monoesters by zirconium(IV) complexes in neutral solution'. Polyhedron, 48 :104-109.
Abstract
Three zirconium(IV) complexes (1-3) with mono- and dinucleating tripodal ligands are reported that promote the hydrolysis of the phosphate monoesters p-nitrophenyl phosphate (NPP) and phenyl phosphate (PP) in neutral solution. At pH 7 up to 10(4)- and 10(6)-fold rate accelerations of the hydrolysis of NPP and PP are observed. A detailed kinetic study has been carried out for NPP. The complexes show Michaelis-Menten behavior, k(cat) and 1/K-m values at pH 7.0, 25 degrees C are 2.7 x 10(-5) s(-1) and 806 M-1 (1), 1.1 x 10(-4) s(-1) and 556 M-1 (2) and 1.1 x 10(-4) s(-1) and 565 M-1 (3). Entropies of activation of -92.0 J K-1 mol(-1) (1), -75.6 J K-1 mol(-1) (2) and -98.6 J K-1 mol(-1) (3) are consistent with an associative mechanism.
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http://dx.doi.org/10.1016/j.poly.2012.09.015
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Attribution-NonCommercial-NoDerivs 3.0 Ireland
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School of Chemistry (Scholarly Articles)