A mononucleating (HL1) and a dinucleating (HL2) “endoff”\ud compartmental ligand have been designed and synthesized by\ud controlled Mannich reaction using p-cresol and bis(2-methoxyethyl)amine,\ud and their formation has been rationalized. Six complexes have been\ud prepared on treating HL1 and HL2 with ZnIIX2 (X = Cl−, Br−, I−) with the\ud aim to investigate their hydrolytic activity on phosphoester bond cleavage.\ud Interestingly, the mononucleating ligand was observed to yield dinuclear\ud complexes, [Zn2(L1)2X2] (1−3), while the potential dinucleating ligand\ud generated mononuclear complexes, [Zn(HL2)X2] (4−6). Four (1−4), out\ud of six complexes studied, were characterized by single-crystal X-ray\ud diffraction (XRD): the Zn ion exhibits trigonal bipyramidal and tetrahedral\ud coordination spheres in the di- and mononuclear complex, respectively.\ud The hydrolytic kinetics, followed spectrophotometrically with 4-nitrophenylphosphate\ud (4-NPP) in buffered dimethylformamide (DMF) (97.5% DMF, v/v) because of solubility reasons, under excess\ud substrate conditions (substrate:complex = 20:1), indicated that the complexes enormously accelerate the rate of\ud phosphomonoester hydrolysis with first order rate constants (kcat) in the range 2−10 s−1 at 25 °C. In each case kinetic data\ud analyses have been run by Michaelis−Menten treatment. The efficacy in the order of conversion of substrate to product (pnitrophenolate\ud ion) follows the trend 1 > 2 > 3 > 4 > 5 > 6, and the ratio of kcat of an analogous dinuclear to mononuclear\ud complex is ≃2. An electrospray ionization-mass spectrometry (ESI-MS) study has revealed the dissociation of the\ud centrosymmetric dinuclear complex to two mononuclear species instead of a syn-cooperative catalysis. Density functional\ud theory (DFT) calculations have been performed to rationalize our proposed mechanistic pathway for phosphatase activity. The\ud comparative analysis concludes the following facts under experimental conditions: (1) the halide bound to the active site affects\ud the overall rate in the order: Cl− > Br− > I− regardless of nuclearity; (2) dinuclear complexes prevail over the mononuclear ones
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