尾式卟啉铁轴向加合含氮配体的共振拉曼光谱的研究  

Iron-Ligand Stretching Band in the Resonace Raman Spectra of a New Tailed Porphyrin Iron (Ⅲ)Complexes with a Series of Axial Ligands

作　　者：赵东源[1] 任继尧[1] 王起斌 修正坤 曹锡章 

机构地区：[1]沈阳化工学院 [2]吉林大学

出　　处：《沈阳化工学院学报》1992年第1期32-40,共9页Journal of Shenyang Institute of Chemical Technolgy

摘　　要：测定了尾式卟啉[5-邻-(4-二甲胺基丁酰胺)苯基-10,15,20-三苯基卟啉](简记 meso-MDMBPTPPH_2)、尾式卟啉铁配合物及其轴向与咪唑、吡啶、三乙胺、二乙胺、乙胺、正丙胺、正丁胺含 N 配体加合物的共振拉曼光谱.详细指认了其振动谱带,考察了轴向配体的改变对 Fe—N 键拉曼伸缩振动的影响.实验结果表明:尾式卟啉尾端侧链的存在,阻碍了苯环的旋转,使苯环与卟啉环相互作用减弱,Raman 光谱产生分裂.1363 cm^(-1)强的振动谱带的出现,证实了尾式卟啉铁是高自旋状态.轴向配体对 Fe—N 伸缩振动谱带有较大的影响,其频率有:咪唑>有机胺>吡啶的规律,同时与轴向配位平衡常数之间存在着:v=8.9log K+338的关系.Resonance Raman spectra of a new rafted Porphyrm iron(Ⅲ)complexes,meso-mono [o—(4-dimethyl amino butylamidophenyl]triphenylporphyrin iron (Ⅲ)chloride and its adducts with a series of axial ligands such as imidazole,pyridine piperidine,Et_3N,Et_2NH, EtNH_2,n-C_3H_7NH_2,n-C_4H_9NH_2,Were observed over 457.9 nm.The band of 1363 cm^(-1) is associated with the nature oxidation[Fe(Ⅲ)]and spin state (high-spin) of ferric com- plex.The bands near 350 cm^(-1)were assigned to Fe-N (axial)stretching modes by the changing of axial ligands.The axial ligands effect on the frequency of the Fe-N stretch- ing modes.The Fe—N (axial)stretching frequencies and the Fe—ligands (axial)forma- tion constants fit the following relationship,v=8.9logK+338

关 键 词：卟啉 拉曼光谱 尾式卟啉 轴向配体 

分 类 号：O626.13[理学—有机化学]