Eu(Ⅲ)与Hbbimp的配合物的合成、表征及与活化磷酸二酯键模型物BDNPP的水解动力学研究

Synthesis and Characterization of Bieuropium Complex Coordinating Hbbimp, and Its Hydrolytic Kinetic Research for Cleaving an Activated Phosphate Diester BDNPP

合成了Eu(Ⅲ)配合物[Eu2(bbimp)(CH3COO)(CH3CH2O)2(CH3CH2OH)](ClO4)2(A),产物经IR谱、UV谱、1HNMR谱、摩尔电导、元素分析对其结构进行了基本鉴定。用紫外光谱法研究了磷酸二酯键模型物双 (2,4 二硝基苯基)磷酸盐BDNPP与配合物A在pH7.26,25和37℃时,[BDNPP]=[A]=2.5×10-5mol·L-1时的动力学性质,得到BDNPP的二级水解速率常数为k25℃=3.027×103(mol·L-1)-1·min-1,k37℃=6.060×103(mol·L-1)-1·min-1,半衰期t1 2分别为12.9和6.6min,使BDNPP的水解速率大大提高。

(ClO_4)_2 (A) was synthesized and characterized by infrared spectra, nuclear magnetic resonance spectra, UV-Vis spectra, molar electrolytic conductivity and elemental analysis. The reactions of A for cleaving bis(2,4-dinitrophenyL)phosphate (BDNPP) was studied with UV-Vis spectra(at ==2.5×10^(-5) mol·L^(-1), pH 7.26, 25 and (37 ℃)), and the second-order rate constants k of 3027×10~3 (mol·L^(-1))^(-1)·min^(-1)(25 ℃) and 6.060×10~3(mol·L^(-1))^(-1)·min^(-1)((37 ℃)) were obtained. Their values of half-life are 12.9 min and 6.6 min, respectively. The results also show that the participation of A rare earths greatly increases BDNPP hydrolytic rate.