Abstract: This paper reports the catalytic properties of “porphyrin-like” Schiff base mononuclear complexes MH2L {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 cyclohexane monooxygenation with PhIO and magnetic properties of the dinuclear complexes. The magnetic investigations (4~300 K) of the dinuclear complexes revealed that their antiferromagnetic spin exchange with J ranged from -10.49 to -0.482 cm-1 except MnZnL and antiferromagnetic spin exchange decreased in the following order: MnⅡ-CuⅡ > MnⅡ-NiⅡ > MnⅡ-MnⅡ > MnⅡ-FeⅢ > MnⅡ-CoⅡ > MnⅡ-CrⅢ. The results of catalyzed oxidation of cyclohexane indicated that the catalytic property of the dinuclear complex was better than that of the corresponding mononuclear complex. It was found that there was the synergism decreased in the order: Mn-Fe > Mn-Cr > Mn-Cu > Mn-Mn > Mn-Co> Mn-Ni > Mn-Zn. It seems that this synergism increases with the increase of the number of unpaired d electrons and the magnetic exchange between the two metals in these dinuclear complexes. |
陈新斌,胡新娟,孙咏芬,陈俊琛,朱瑞荣,桑言奎,廖代正,朱申杰.Schiff 碱双核配合物的磁性及催化性能的研究[J].无机化学学报,2005,21(8):1208-1212. |