Conformational control of [26]hexaphyrins(1.1.1.1.1.1) by meso-thienyl substituents
Conformational control of [26]hexaphyrins(1.1.1.1.1.1) by meso-thienyl substituents
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DOI：
10.1002/chem.200601147
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Osuka, Atsuhiro
中科院分区：
文献类型：
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作者：
Suzuki, Masaaki;Osuka, Atsuhiro
内消旋芳基取代的[26]己卟啉（1.1.1.1.1）（[26]ArH）的构象偏好和化学稳定性取决于内消旋芳基取代基。虽然到目前为止，[26]ArH仅被鉴定为平面和矩形构象（II型构象），但我们在这里已经证明，对于在15-和30-位上具有小的2-噻吩基或3-噻吩基取代基的[26]ArH（7和11-I），优选所有吡咯指向内部的不同构象（I型构象）。I型和II型[26]ArH都表现出diatropic环电流，反映了芳香族特征。I型[26]ArH，如7和11-I，已被证明可作为Pd-II离子的有效配体，通过容易的C-H键活化提供具有N3 Cl配位的双-Pd-II络合物12和13。
Conformational preference and chemical stability of meso-aryl-substituted [26]hexaphyrins(1.1.1.1.1.1) ([26]ArH) depend upon meso-aryl substituents. Although only a planar and rectangular conformation (type-II conformation) has been identified for [26]ArH so far, we have demonstrated here that a different conformation with all the pyrroles pointing inward (type-I conformation) is preferred for [26]ArH (7 and 11-I) bearing small 2-thienyl or 3-thineyl substituents at 15- and 30-positions. Both type-I and type-II [26]ArH exhibit diatropic ring currents, reflecting aromatic character. Type-I [26]ArH, such as 7 and 11-I, have been shown to serve as an effective ligand for Pd-II ions to provide bis-Pd-II complexes 12 and 13 with N3C1 coordination through facile C-H bond activation.