Abstract:
The chiral properties of nickel(II) complexes of porphyrin-porphyrin Tröger\'s base and porphyrin-chlorin spiro-Tröger\'s base with phenyl or 3-methoxyphenyl substitutions in their meso-positions were studied. Enantioseparation of racemic mixtures was investigated via high-performance liquid chromatography (HPLC) on an analytical ReproSil Chiral-NR column. The optimal conditions were utilized for a multimilligram scale isolation with a semipreparative column. The purity of the isolated enantiomers was determined by HPLC and UV-Vis spectroscopy. The absolute configurations of the isolated enantiomers were determined by evaluating the Cotton effect in electronic circular dichroism spectra. The determination was supported by TDDFT calculations, in which good agreement was achieved between the experimental and simulated spectra. The maximum molar ellipticity values, [θ]λmax given in deg ∙ cm2 ∙ dmol-1, were [θ]435 = 1.73 ∙ 107 for phenyl spiroTB and [θ]436 = 1.24 ∙ 107 and [θ]436 = 2.15 ∙ 107 for 3-methoxyphenyl TB and spiroTB, respectively.
摘要:
研究了卟啉-卟啉Tröger碱和卟啉-二氢卟啉螺-Tröger碱的镍(II)配合物的手性,其内消旋位置具有苯基或3-甲氧基苯基取代基。通过高效液相色谱(HPLC)在分析性ReproSil手性-NR柱上研究了外消旋混合物的对映体分离。最佳条件用于半制备色谱柱的多毫克规模分离。通过HPLC和UV-Vis光谱法测定分离的对映体的纯度。通过评估电子圆二色性光谱中的Cotton效应来确定分离的对映体的绝对构型。该确定得到了TDDFT计算的支持,其中实验和模拟光谱之间达到了很好的一致性。最大摩尔椭圆率值,[θ]λmax,单位为deg•cm2•dmol-1,苯基螺TB为[θ]435=1.73•107,3-甲氧基苯基TB为[θ]436=1.24•107和[θ]436=2.15•107,分别。