Raman and IR Spectroscopic Analysis of Substituted Tetraphenylporphyrin Iron Complexes
WANG Lan-zhi1,2,SHE Yuan-bin2*
1. College of Chemistry & Material Science, Hebei Normal University, Shijiazhuang 050011, China 2. Institute of Green Chemistry and Fine Chemicals, Beijing University of Technology, Beijing 100122, China
Abstract：In the present paper, two series of substituted tetraphenylporphyrin iron compounds RTPPFe(Ⅱ) and RTPPFeCI(Ⅲ) were synthesized by two-step synthetic method. Raman and IR spectra of tetraphenylporphyrin iron complexes were investigated. By analyzing the IR and Raman spectra of RTPPFe(Ⅱ) and RTPPFe(Ⅲ)Cl, it was confirmed that the RTPPFe(Ⅱ) complexes were usually unstable at normal temperature and existed via the coordination of dioxygen with the iron (Ⅱ) center, i.e. they formed into TPPFe-O2,and the stable configuration of dioxygen with the iron (Ⅱ) center was “end-on”. In addition, the geometric structure optimization of substituted iron tetraphenylporphyrin complexes was performed by PM3 semi-empirical and MM+ method quantum calculation. The structure parameters were obtained, including EHOMO,ELUMO and total energy, bond length of Fe—Cl etc. The effect of molecular structure on vibrational frequency shift was studied by combing the IR and Raman spectra. The results showed that for iron tetraphenylporphyrins (RTPPFe-O2) with different structure, the vibrational frequencies of the Fe—O bond were associated with their twist degree of molecular structures, i.e. the Raman and IR characterization vibrational frequencies of the Fe—O2 were up shifted with the increase in the Fe—O—O angle of iron tetraphenylporphyrins (RTPPFe-O2) molecule.
王兰芝1,2,佘远斌2* . 取代铁卟啉的拉曼及红外光谱分析[J]. 光谱学与光谱分析, 2009, 29(03): 694-697.
WANG Lan-zhi1,2,SHE Yuan-bin2*. Raman and IR Spectroscopic Analysis of Substituted Tetraphenylporphyrin Iron Complexes. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2009, 29(03): 694-697.
[1] WANG Rong, ZHENG Rong-er, LI Ying, et al(王 荣, 郑荣儿, 李 颖, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2005, 25(4): 604. [2] CHEN Bi-fang, LIU Tian-fu(陈碧芳, 刘天夫). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2006, 26(8): 1513. [3] CHEN Ying, YAO Min-na, TANG Yao-ji, et al(陈 莹，姚敏娜，唐尧基，等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2005, 25(12): 2048. [4] XU Yan, AN Qing-da, ZHANG Shao-yin, et al(许 艳, 安庆大, 张绍印, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2006, 26(6): 1134. [5] Wang L Z, She Y B, Zhong R G, et al. Organic Process Research & Development, 2006, 10(4): 757. [6] Davydov R, Makris T, et al. J. Am. Chem. Soc., 2001, 123: 1403. [7] Groves J T W, Kruper J, Nemo T E, et al. J. Mol. Catal., 1980, 7(2): 169. [8] GUO Can-cheng, HE Xing-tao, ZOU Gang-yao(郭灿城, 何兴涛, 邹纲要). Chin. J. Org. Chem.(有机化学), 1991, 11(4): 416. [9] Guo C C, Peng Q J, Liu Q, et al. J. Mol. Catal., 2003, 192: 295. [10] Burke J M, Kincaid J R, Peters S, et al. J. Am. Chem. Soc., 1978, 100(19): 6083. [11] Alain D, Michel M, Marc L. Inorg. Chem., 1989, 28: 825. [12] Leonard M P, Insook R P, Kazuo N. J. Am. Chem. Soc., 1991, 113: 3294.
