NMR STUDIES OF NONPLANAR PORPHYRINS. PART 1. AXIAL LIGAND ORIENTATIONS IN HIGHLY NONPLANAR PORPHYRINS-猫眼课题宝

非平面卟啉的核磁共振研究。

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2010

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作者：

C. Medforth;C. Muzzi;K. Shea;Kevin M Smith;R. J. Abraham;S. Jia;J. Shelnutt

非平面卟啉配合物中的配体取向对1a-e和2a-e进行了分子研究力学计算和质子核磁共振波谱。最小能量计算的络合物1a-e的结构表明，轴向的吡啶或咪唑配体大致定向与CoIII-Nporrin键平行，其中配体环平面彼此垂直。为配合物2a-e，计算的轴向配位体的平面最小能量结构沿卟啉取向。介观碳轴和配位环平面为彼此垂直的。因此，对于这两个系列的复合体，轴向配体的平面定向为平行于所形成的腔由这些非常不平坦的卟啉。质子核磁共振研究表明类似于从分子力学中得到的结构计算保留在解决方案中。在一些建筑群中，受阻还观察到了轴向配体的旋转。络合物1a-e和 2a-e是卟啉构象的不寻常的例子影响轴向配体的取向，因此可能是可用作研究配体取向效应的模型生物系统。

The ligand orientations in the nonplanar porphyrin complexes 1a–e and 2a–e have been investigated using molecular mechanics calculations and proton NMR spectroscopy. The minimum energy structures calculated for complexes 1a–e show that the planes of the axial pyridine or imidazole ligands are orientated approximately parallel to the CoIII–Nporphyrin bonds, with the ligand ring planes being perpendicular to each other. For complexes 2a–e, the planes of the axial ligands in the calculated minimum energy structures are orientated along the porphyrin meso carbon axis and the ligand ring planes are perpendicular to each other. Thus, for both series of complexes the planes of the axial ligands are orientated parallel to cavities formed by these very nonplanar porphyrins. Proton NMR studies suggest that structures similar to those obtained from the molecular mechanics calculations are retained in solution. In some complexes, hindered rotation of the axial ligands is also observed. Complexes 1a–e and 2a–e are unusual examples of the porphyrin conformation influencing the orientations of axial ligands and, as such, may be useful as models for studying ligand orientation effects in relation to biological systems.

NMR STUDIES OF NONPLANAR PORPHYRINS. PART 1. AXIAL LIGAND ORIENTATIONS IN HIGHLY NONPLANAR PORPHYRINS

非平面卟啉的核磁共振研究。

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