甲烷单加氧酶的模型化合物:以树脂为载体的双铁(Ⅲ)催化剂的合成、表征及催化性能的研究

使用树脂为载体,合成了6种新的双铁(Ⅲ)催化剂,成功的模拟了可溶性甲烷单加氧酶(MMO)的双核铁中心.这是首次使用树脂作为载体合成模拟MMO的非均相催化剂.在室温下以乙腈为溶剂,30%的过氧化氢或特丁基过氧化氢做氧化剂,环己烷或乙苯作为底物的反应中,催化剂具有MMO相似的催化活性.其中,使用大孔氨甲基树脂为载体合成的催化剂能有效地催化乙苯氧化得到较好的转化率(总收率达69.9%,TON值达55.3).同时研究了树脂的颗粒大小及阴离子供体对催化性能的影响.使用粒径0.675～0.280 mm的树脂和ClO-4的阴离子供体所合成的催化剂具有很好的催化活性.最后探讨了催化剂的回收和再利用.

Synthesis,Characterization and Catalytic Activity of Resin-based Diiron (Ⅲ) Catalysts:Model for Methane Monooxygenase

Six novel resin-based μ-oxo diiron (Ⅲ) catalysts have been successfully prepared to model the functional properties of Fe2O enzyme methane monooxygenase (MMO).The catalysts were characterized and exhibited the monooxyge-nase-like ability to oxidize cyclohexane or ethylbenzene to responding alcohols and ketones in acetonitrile at room temperature by 30 % hydroperoxide (H2O2) or tert-butyl hydroperoxide (TBHP) as the oxidant.The catalyst prepared through macroporous aminomethyl resin showed the most efficient in the catalytic oxidation of ethylbenzene with moderate yields (total yield up to 69.9 %,turnover number 55.3).The effects of the particle size of resins and the anion donor were also studied,showing that the perchlorate anion is better than chloride and nitrate.The most efficient catalytic activity was observed by the catalyst synthesized through particle size 0.675-0.280 nm of resin and ClO-4.Furthermore,the catalysts show a potential for recover and reuse.