含聚醚链的Schiff碱锰(III)配合物在胶束溶液中催化BNPP水解反应的研究

合成了两种新的聚醚取代的水杨醛亚胺Schiff碱锰(III)配合物MnL12Cl和MnL2Cl,研究了它们与表面活性剂2Brij35形成的金属胶束对BNPP的催化水解反应.探讨了催化反应机理,提出了水解反应的动力学数学模型;计算了催化反应的Michanelis常数和表观活化能,并与不含聚醚链的类似物MnL2Cl比较,考查了配合物配体中聚醚支链及其3端基对催化水解反应的影响.结果表明,催化水解反应遵循金属-氢氧离子机理;以羟基作为聚醚链端基的MnL12Cl的催化活性最高,在相同条件下,其表观一级速率常数约为MnL2Cl的3倍,为MnL2Cl的30倍.23

Study of the BNPP Hydrolysis Catalyzed by the Schiff Base Magnesium(III) Complexes Bearing Polyether Side Chains in the Micelle Solution

Two new Schiff base Mn(III) complexes ( MnL12Cl and MnL2Cl) containing polyether side 2 chains were prepared and used in BNPP hydrolysis as catalyst of metallomicelle resulting from the reaction with Brij35. The mechanism of the catalytic hydrolysis reaction was discussed, a kinetic mathematical model of BNPP cleavage catalyzed by the metallomicelle was proposed, and the Michanelis constant and the ap- parent active energy of the catalytic reaction were calculated. Compared with polyether side chain-free analogues MnL32Cl , the effect of polyether side chains and their terminal groups on catalytic hydrolysis reaction was investigated. The result showed that the catalytic reaction obeyed the mechanism of the metal-hydroxide, and the activity of MnL12Cl , which contains hydroxyl group OH as the terminal group of the polyether side chain, is the highest. Under the same condition, the pseudo-first-order rate constant kobs (s-1) of BNPP hydrolysis catalyzed by MnL12Cl is about 3 times that of MnL2Cl, and about 30 times that 2 of MnL32Cl , respectively.