Porphyrin(2.1.2.1) rhenium(I) complexes: Synthesis, structures, properties, and dipyrrin act as bipyridyl-like ligand
Porphyrin(2.1.2.1) rhenium(I) complexes: Synthesis, structures, properties, and dipyrrin act as bipyridyl-like ligand
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DOI：
10.1080/00958972.2022.2146498
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发表时间：
2022-11
影响因子：
1.9
通讯作者：
Songlin Xue;Xiao-Meng Lv;Ningchao Liu;Hirofumi Morimoto;Bentian Xiao;N. Aratani;Daiki Kuzuhara;H. Yamada;F. Qiu
中科院分区：
文献类型：
--
作者：
Songlin Xue;Xiao-Meng Lv;Ningchao Liu;Hirofumi Morimoto;Bentian Xiao;N. Aratani;Daiki Kuzuhara;H. Yamada;F. Qiu
摘要 两个新的铼(I)卟啉配合物(H2PY: 3,3-铼(I)三甲酰氯-(31 E,32 Z,71 E,72 Z)-4,8-双(全氟苯基)-11 H,32 H,72 H-51 λ2 ,71 λ4 -1,5(2,5),3,7(5,2)-四吡咯-2,6(1,2)-二苯并环辛烷和H2PZ：3,3-乙酸三羰基铼(I)-(31 E,32 Z,71 E,72 Z)-4,8-双(全氟苯基)-11 H,32 H,72 H-51 λ2 ,71含有两个不同Re(I)−N π键网络的λ4 -1,5(2,5),3,7(5,2)-四吡咯-2,6(1,2)-二苯并环辛烷)由在两个中间位置带有五氟苯基取代基的鞍形卟啉(2.1.2.1)制备(H2Por: 31 E,32 Z,71 E,72Z)-4,8-双(全氟苯基)-11H,32H,51H,72H-1,5(2,5),3,7(5,2)-四吡咯-2,6(1,2)-二苯并环辛烷)。尽管卟啉(2.1.2.1)支架具有四吡咯性质，但这是吡咯基大环化合物在形成八面体Re(I)配合物时充当类联吡啶配合物配体的第一个案例。 X 射线分析和 1H NMR 研究表明，两种 Re(I) 配合物（H2PY 和 H2PZ）均由一个与二吡啉单元 π 键合的八面体 Re(I) 离子和一个通过邻亚苯基桥连接在一起的质子化二吡啉部分组成。将这种键合行为与卟啉(2.1.2.1)大环化合物以及其他Re(I)卟啉的相关金属配合物进行比较，并证明H2Por的扭曲构象和电子学可以作为检查与其他相关平面卟啉大环化合物不同的结构性质关系的新平台。图解摘要
Abstract Two new rhenium(I) porphyriniod complexes (H2PY: 3,3-rhenium(I) tricarbonyl chloride-(31 E,32 Z,71 E,72 Z)-4,8-bis(perfluorophenyl)-11 H,32 H,72 H-51 λ2 ,71 λ4 -1,5(2,5),3,7(5,2)-tetrapyrrola-2,6(1,2)-dibenzenacyclooctaphane, and H2PZ: 3,3-rhenium(I) tricarbonyl acetate-(31 E,32 Z,71 E,72 Z)-4,8-bis(perfluorophenyl)-11 H,32 H,72 H-51 λ2 ,71 λ4 -1,5(2,5),3,7(5,2)-tetrapyrrola-2,6(1,2)-dibenzenacyclooctaphane) containing two different Re(I)−N π-bonding networks were prepared from the saddle-shaped porphyrin(2.1.2.1) bearing pentafluorophenyl substituents at the two meso-positions (H2Por: 31 E,32 Z,71 E,72 Z)-4,8-bis(perfluorophenyl)-11 H,32 H,51 H,72 H-1,5(2,5),3,7(5,2)-tetrapyrrola-2,6(1,2)-dibenzenacyclooctaphane). Despite the tetrapyrrolic nature of the porphyrin(2.1.2.1) scaffold, this is the first case of a pyrrole-based macrocycle which acts as a bipyridyl-like complexing ligand in the formation of an octahedral Re(I) complex. X-ray analysis and 1H NMR studies show that both Re(I) complexes (H2PY and H2PZ) consist of one octahedral Re(I) ion π-bonded to a dipyrrin unit and one protonated dipyrrin moiety linked together through o-phenylene bridges. This bonding behavior is compared to related metal complexes of porphyrin(2.1.2.1) macrocycles as well as other Re(I) porphyrins and demonstrates that the distorted conformation and, by virtue, the electronics of H2Por serve as a novel platform for examining structure property relationships which differ than those of other related planar porphyrin macrocycles. Graphical Abstract