Acta Chimica Sinica ›› 1996, Vol. 54 ›› Issue (3): 304-312. Previous Articles    

Original Articles

双核铜蛋白模型化合物的合成、氧合和催化苯偶姻的氧化

鄢家明;谢如刚;赵华明   

  1. 四川大学化学系
  • 发布日期:1996-03-15

The synthesis of binuclear copper protein models, oxygenation and catalytic oxidation of benzoin

YAN JIAMING;XIE RUGANG;ZHAO HUAMING   

  • Published:1996-03-15

New ligands (3~9) containing four imidazolyls have been prepared efficiently by 2,6-bis(imidazolymethyl)- 4-chlorophenol reaction with 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane or α,α'- dibromo-m-xylene. New binuclear copper protein models (10~16) in which two imidazolyls coordinate with each copper ion have been prepared also from the reaction of [Cu(CH~3CN)~4]ClO~4 with ligands. The oxygenation of models has been studied. It's discovered that 13 complexes O~2 and inserts one of oxygen atoms into the 2-position of m-xylyl spacer to form a phenolate and hydroxide bridge binuclear copper (Ⅱ) complex, the others react via four electrons reduction of the dioxygen molecule to give bis(μ-hydroxy) copper (Ⅱ) complexes. The oxidation reaction of benzoin under the catalysis of the mimic system composed of the ligand and cuppric salt has been studied kinetically, the influence of basicities, additives and metal ions on reaction rate being examined. It's found that the model composed of 4 in admixture with copper salt partakes efficiency 6 fold higher than that under the catalysis of copper salt alone. The reaction follows Michaelis-Menten saturation kinetic behavior and the kinetic paraments V~m~a~x, k~m are 9.47×10^-^5 mol·dm^-^3·s^-^1 and 0.0418mol·dm^-^3 respectively.

Key words: PHENOL P, IMIDAZOLE P, REACTION KINETICS, COPPER COMPLEX, DINUCLEAR COMPLEX, CATALYTIC OXIDATION, METALLOPROTEIN, MODEL COMPOUND, BENZOIN

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