β-octabromo-meso-tris(pentafluorophenyl)corrole: reductive demetalation-based synthesis of a heretofore inaccessible, perhalogenated free-base corrole
β-octabromo-meso-tris(pentafluorophenyl)corrole: reductive demetalation-based synthesis of a heretofore inaccessible, perhalogenated free-base corrole
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DOI：
10.1142/s1088424610002331
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发表时间：
2010-06-01
影响因子：
1.5
通讯作者：
Ghosh, Abhik
中科院分区：
文献类型：
--
作者：
Capar, Can;Hansen, Lars-Kristian;Ghosh, Abhik
β-八溴-meso-三（五氟苯基）咔咯（H-3[Br 8 TPFPC]）以各种金属络合物形式存在已久，但迄今为止尚未以游离配体形式存在。它可以通过Mn[Br_8TPFPC]的还原脱金属（浓H_2SO_4，FeCl_2）以高产率（86%）制备。有趣的是，相同的条件并没有导致类似的铜络合物的脱金属，这可能与许多其他铜络合物的行为形成对比，这些铜络合物完全脱金属。X射线晶体学分析揭示了一种独特的“半鞍”构象，其中两个吡咯环的一侧上的直接吡咯-吡咯键是强烈倾斜向上和向下相对于彼此，而其他两个吡咯环大致在平均平面的大环。
Long known in various metal-complexed forms, beta-octabromo-meso-tris(pentafluorophenyl) corrole, H-3[Br8TPFPC], has not been available as a free ligand until now. It can be prepared in high yield (86%) via reductive demetalation (conc. H2SO4, FeCl2) of Mn[Br8TPFPC]. Interestingly, the same conditions did not result in demetalation of the analogous copper complex, which may be contrasted to the behavior of many other copper corroles, which demetalate cleanly. X-ray crystallographic analysis revealed a unique "half-saddled" conformation, wherein two of the pyrrole rings on one side of the direct pyrrole-pyrrole linkage are strongly tilted up and down relative to each other, whereas the other two pyrrole rings are roughly in the mean plane of the macrocycle.