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合成表征了酚氧、双羧基桥联双组氨酸的手性双铁核配合物和双锰核配合物,研究了它们催化亚碘酸苯对烯烃的环氧化反应和对环烷烃的羟化反应.结果表明这种Fe_2(Ⅲ)和Mn_2(Ⅲ)配合物均是有效的甲烷单加氧酶(MMO)模型化合物,其中Fe_2配合物能较好地再现MMO的某些性质,如电子光谱等.Fe_2配合物催化苯乙烯环氧化反应生成环氧苯乙烷的产率为840％(以催化剂计),且R-(+)-构型对映体过量(e.e.)达45.4％,相应的Mn_2配合物则以7080％产率给出环氧苯乙烷,R-(+)-构型对映体过量51.6％.Mn_2配合物还能够催化环己烯和环己烷的氧化反应,产物及其分布分别为环氧环己烷3880、环己烯醇603、环己烯酮189和环己醇1053、环己酮639％(以催化剂计).EPR研究表明MM=O是反应的活性中间体.
Synthesis and characterization of phenolic oxygen, dicarboxy-bridged bis-histidine chiral double iron core complexes and dimanganese nuclear complexes were studied, they catalyze the oxidation of iodate benzene and olefins epoxidation reaction of naphthene The results showed that both Fe 2 (Ⅲ) and Mn 2 (Ⅲ) complexes were effective model compounds for methane monooxygenase (MMO), in which Fe 2 complex could better reproduce some properties of MMO such as electron Spectroscopy, etc. The yield of the styrene oxide epoxidation of styrene by the Fe 2 complex was 840% (based on the catalyst), and the enantiomeric excess (ee) of the R - (+) - configuration was 45.4% , Respectively, the corresponding Mn_2 complexes give the styrene oxide in 7080% yield with an enantiomeric excess of R - (+) - configuration of 51.6% .Mn_2 complexes can also catalyze the oxidation of cyclohexene and cyclohexane The reaction product and its distribution were cyclohexene oxide 3880, cyclohexenol 603, cyclohexenone 189 and cyclohexanol 1053, cyclohexanone 639% (based on catalyst) .EPR study showed that MM = O is Reactive reactive intermediates.