Schiff碱双核配合物的磁性及模拟甲烷单加氧酶催化性能的研究  

Magnetic and Biomimetic Catalytic Properties of New Schiff Base Dinuclear Complexes as Model Compounds of Methane Monooxygenase

作　　者：陈新斌[1] 廖代正[2] 孙咏芬[1] 胡新娟[1] 杨艳[1] 朱申杰[2] 

机构地区：[1]上海师范大学生命与环境科学学院,上海200234 [2]南开大学化学系,天津300071

出　　处：《高等学校化学学报》2005年第1期78-80,共3页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 9472 0 5 5 );上海市高等学校科学技术发展基金 (批准号 :0 3 DZ14 )资助

摘　　要：This paper reports the biomimetic catalytic properties of new Schiff base mononuclear complexes MH 2L｛M = Mn(Ⅱ), Fe(Ⅲ)Cl, Cr(Ⅲ)Cl, Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ); L=bis[ N,N′-ethylene-2,2′-(phenylmethylene)bis(3,4-dimethylpyrrole-5-aldimino)]｝and dinuclear complexes MnML[M=Mn(Ⅱ), Fe(Ⅲ)Cl, Cr(Ⅲ)Cl, Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)] for studying the monooxygenation of cyclohexane with PhIO and magnetic properties of the dinuclear complexes. The investigation of the magnetic properties(4—300 K) of the dinuclear complexes revealed that their antiferromagnetic spin exchange with J varied from -10.49 to -0.482 cm -1 except MnZnL, and antiferromagnetic spin exchange decreased in the order: Mn(Ⅱ)-Cu(Ⅱ)>Mn(Ⅱ)-Ni(Ⅱ)>Mn(Ⅱ)-Mn(Ⅱ)>Mn(Ⅱ)- Fe(Ⅲ)>Mn(Ⅱ)-Co(Ⅱ)>Mn(Ⅱ)-Cr(Ⅲ). The yield determination of monooxygenation of cyclohexane indicated that the catalytic reactivity of the dinuclear complex was better than that of the corresponding mononuclear complex, so we supposed that there was some cooperative action between the two metals in these dinuclear complexes. It was found that the cooperation lay in the decreasing order: Mn-{Fe>}Mn-Cr>Mn-Cu>Mn-Mn>Mn-Co>Mn-Ni>Mn-Zn. It seems that this cooperation increased with the increase of the number of unpaired d electrons and the magnetic exchange between the two metals in these dinuclear complexes.This paper reports the biomimetic catalytic properties of new Schiff base mononuclear complexes MH 2L｛M = Mn(Ⅱ), Fe(Ⅲ)Cl, Cr(Ⅲ)Cl, Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ); L=bis[ N,N′-ethylene-2,2′-(phenylmethylene)bis(3,4-dimethylpyrrole-5-aldimino)]｝and dinuclear complexes MnML[M=Mn(Ⅱ), Fe(Ⅲ)Cl, Cr(Ⅲ)Cl, Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)] for studying the monooxygenation of cyclohexane with PhIO and magnetic properties of the dinuclear complexes. The investigation of the magnetic properties(4—300 K) of the dinuclear complexes revealed that their antiferromagnetic spin exchange with J varied from -10.49 to -0.482 cm -1 except MnZnL, and antiferromagnetic spin exchange decreased in the order: Mn(Ⅱ)-Cu(Ⅱ)>Mn(Ⅱ)-Ni(Ⅱ)>Mn(Ⅱ)-Mn(Ⅱ)>Mn(Ⅱ)- Fe(Ⅲ)>Mn(Ⅱ)-Co(Ⅱ)>Mn(Ⅱ)-Cr(Ⅲ). The yield determination of monooxygenation of cyclohexane indicated that the catalytic reactivity of the dinuclear complex was better than that of the corresponding mononuclear complex, so we supposed that there was some cooperative action between the two metals in these dinuclear complexes. It was found that the cooperation lay in the decreasing order: Mn-{Fe>}Mn-Cr>Mn-Cu>Mn-Mn>Mn-Co>Mn-Ni>Mn-Zn. It seems that this cooperation increased with the increase of the number of unpaired d electrons and the magnetic exchange between the two metals in these dinuclear complexes.

关 键 词：SCHIFF碱 双核配合物 磁交换作用 拟酶催化 协同作用 

分 类 号：O627.7[理学—有机化学]