Axial Coordination Reactions of Substitutive Derivates of Manganese Porphyrins and Determination of Equilibrium Constants
摘 要
研究了4种具有不同取代基的锰卟啉在三氯甲烷溶剂中与咪唑(Im)、4-甲基咪唑(4-MeIm)、吡啶(Py)、4-甲基吡啶(4-MePy)等4种客体小分子的轴向配位反应,并采用微量紫外-可见光谱滴定法测定了反应的平衡常数。结果表明:每种锰卟啉均可以与咪唑及吡啶类客体分子发生轴向配位反应,轴向配合物的形成能力和稳定性与锰卟啉所含有的取代基有关,在β位上含有强吸电子硝基取代基的锰卟啉与客体分子能够形成更稳定的配合物;客体分子的性质对轴向配合物的形成也有显著的影响,锰卟啉与吡啶以物质的量之比为1:1反应生成五元配位化合物;每一种锰卟啉与其他3种客体分子均以物质的量之比为1:2反应生成六元配位化合物。客体的轴向配位反应能力由大到小依次为Im、4-MeIm、4-MePy、Py。
Abstract
Axial coordination reactions between 4 substitutive derivates of manganese porphyrins and 4 small molecular ligands of imidazole (Im), 4-methylimidazole (4-MeIm), pyridine (Py) and 4-methylpyridine (4-MePy) in CHCl3 medium were studied and the equilibrium constants of the coordination reactions were determined by micro UV-Vis spectrophotometric titration. It was found that each of the 4 manganese porphyrins with different substitution forms coordination complex with either of the 4 guest ligands, with their formation ability and stability related to the position of substituents in the manganese porphyrin molecules. The manganese porphyrins with substitution of -NO2- group at the β position, form more stable complexes with the guest ligands due to the strong electron affinity of the NO2- group; different structures of the guest ligands also show significant effects on the coordination reaction. A 5-membered complex with mole ratio of manganese porphyrins and pyridine of 1 to 1 is formed; and 6-membered complexes with mole ratio of manganese porphyrins and the remainder 3 guest ligands of 1 to 2 are formed. Reaction abilities of the 4 guest ligands in the coordination reactions have the following order:Im > 4-MeIm > 4-MePy > Py.
中图分类号 O657.32 DOI 10.11973/lhjy-hx201708014
所属栏目 工作简报
基金项目 国家自然科学基金(21501070);江苏大学高级人才基金(05JDG051;15JDG131)
收稿日期 2017/1/31
修改稿日期
网络出版日期
作者单位点击查看
备注侯月平(1975-),女,江苏镇江人,副教授,主要从事化工分析的教学和研究工作
引用该论文: HOU Yueping,CHEN Xueyan,FANG Yuanyuan,OU Zhongping. Axial Coordination Reactions of Substitutive Derivates of Manganese Porphyrins and Determination of Equilibrium Constants[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2017, 53(8): 933~937
侯月平,陈雪雁,房媛媛,欧忠平. 取代锰卟啉的轴向配位反应及平衡常数的测定[J]. 理化检验-化学分册, 2017, 53(8): 933~937
共有人对该论文发表了看法,其中:
人认为该论文很差
人认为该论文较差
人认为该论文一般
人认为该论文较好
人认为该论文很好
参考文献
【1】KADISH K M, GUILARD R, SMITH K M. The porphyrin handbook[M]. San Diego:Academic Press, 2000.
【2】KADISH K M, GUILARD R, SMITH K M. Handbook of porphyrin science[M]. New Jersey:World Scientific, 2016.
【3】KADISH K M, GUILARD R, SMITH K M. The porphyrin handbook[M]. San Diego:Academic Press, 2000.
【4】ELLIS P E J, LINARD J E, SZYMANSKI T, et al. Axial ligation constants of iron(Ⅱ) and cobalt(Ⅱ) "capped" porphyrins[J]. Journal of the American Chemical Society, 1980,102:1889-1896.
【5】王树军.羟基锌卟啉轴向配位反应的光谱性质研究[J].分子科学学报, 2009,25(6):431-435.
【6】邵迎,朱志昂,阮文娟,等.非对称取代卟啉钴(Ⅱ)轴向配位反应的热力学研究[J].高等学校化学学报, 1997,18(10):1571-1575.
【7】倪春林.新型尾式色氨酸四苯基卟啉铁(Ⅲ)与咪唑轴向配位反应热力学研究[J].化学世界, 2000,41(9):470-472.
【8】YANG S B, SUN B, OU Z P, et al. β-Nitro-substituted free-base, iron(Ⅲ) and manganese(Ⅲ) tetraarylporphyrins:Synthesis, electrochemistry and effect of the NO2 substituent on spectra and redox potentials in non-aqueous media[J]. Journal of Porphyrins and Phthalocyanines, 2013,17:857-869.
【2】KADISH K M, GUILARD R, SMITH K M. Handbook of porphyrin science[M]. New Jersey:World Scientific, 2016.
【3】KADISH K M, GUILARD R, SMITH K M. The porphyrin handbook[M]. San Diego:Academic Press, 2000.
【4】ELLIS P E J, LINARD J E, SZYMANSKI T, et al. Axial ligation constants of iron(Ⅱ) and cobalt(Ⅱ) "capped" porphyrins[J]. Journal of the American Chemical Society, 1980,102:1889-1896.
【5】王树军.羟基锌卟啉轴向配位反应的光谱性质研究[J].分子科学学报, 2009,25(6):431-435.
【6】邵迎,朱志昂,阮文娟,等.非对称取代卟啉钴(Ⅱ)轴向配位反应的热力学研究[J].高等学校化学学报, 1997,18(10):1571-1575.
【7】倪春林.新型尾式色氨酸四苯基卟啉铁(Ⅲ)与咪唑轴向配位反应热力学研究[J].化学世界, 2000,41(9):470-472.
【8】YANG S B, SUN B, OU Z P, et al. β-Nitro-substituted free-base, iron(Ⅲ) and manganese(Ⅲ) tetraarylporphyrins:Synthesis, electrochemistry and effect of the NO2 substituent on spectra and redox potentials in non-aqueous media[J]. Journal of Porphyrins and Phthalocyanines, 2013,17:857-869.
相关信息
标题 | 相关频次 | |
微量光度滴定法测定咔咯化合物的质子化和去质子化常数 | 2 | |
多溴代苯基荧光酮光度法测定纯锌中痕量铅 | 1 | |
二溴四苯基卟啉分光光度法测定水样中铅 | 1 | |
石灰混凝澄清处理产出水输送管道的腐蚀失效原因 | 1 | |
一种多卤代苯基荧光酮显色剂的合成及分光光度法测定微量镉 | 1 |