Add time:07/19/2019         Source:sciencedirect.com

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 104- and 106-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, kcat and 1/Km values at pH 7.0, 25 °C are 2.7 × 10−5 s−1 and 806 M−1 (1), 1.1 × 10−4 s−1 and 556 M−1 (2) and 1.1 × 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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