η5-Cyclopentadienyliron(II)-[14]triphyrin(2.1.1) sandwich compounds: synthesis, characterization, and stable redox interconversion.
η5-Cyclopentadienyliron(II)-[14]triphyrin(2.1.1) sandwich compounds: synthesis, characterization, and stable redox interconversion.
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DOI：
10.1002/anie.201302815
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发表时间：
2013-07
影响因子：
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通讯作者：
Zhaoli Xue;Daiki Kuzuhara;S. Ikeda;Yuka Sakakibara;K. Ohkubo;N. Aratani;T. Okujima;H. Uno;S. Fukuzumi;H. Yamada
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文献类型：
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作者：
Zhaoli Xue;Daiki Kuzuhara;S. Ikeda;Yuka Sakakibara;K. Ohkubo;N. Aratani;T. Okujima;H. Uno;S. Fukuzumi;H. Yamada
二茂铁，一个铁（II）中心夹在一对芳香族的茂金属（Cp）配体之间，是1951年发现的第一个已知的和典型的茂金属。此后，对二茂铁类化合物的研究在氧化还原介体、催化剂、电子给体、转动铰链部分等多个领域得到了迅速发展，但由于p-扩展的Cp型配体配位能力较弱，迄今为止对具有单价阴离子特征的大环p-共轭体系的研究报道较少。特别是在卟啉家族中，有几种卟啉化合物的研究报道：（1）Cp-Sc-卟啉，Cp-Zr-卟啉，Cp*-Ru-卟啉（Cp* =五甲基卟啉），尽管卟啉和卟啉是二价配体;（2）B，b ′-稠合单钌茂基卟啉，双二茂铁卟啉，具有五元环部分的亚酞菁的金属卟啉和环戊二烯基钌P配合物（吡咯或环己二烯部分）作为配体。最近才报道了二硫乙炔卟啉和N-稠合卟啉（NFP）的双层铁（II）配合物，其中它们表现为具有单个负电荷的大环三齿配体。在NFP复合物的合成过程中，他们通过质谱检测到Cp-Fe-NFP化合物，该化合物尚未分离。迄今为止，Cp-Fe-卟啉夹心化合物的合成仍然是一个相当大的挑战。在2008年，我们报道了一种简便的合成[14]triphyrin（2.1.1）（TriP，1）的方法，作为无硼缩环卟啉的第一个例子。与报道的圆顶形硼亚卟啉配合物相比，这些新的卟啉类化合物开辟了一条通往以前未探索的收缩卟啉类化合物配位化学区域的道路，作为单阴离子环状三齿配体。由于大环的灵活性，TriP已经实现了八面体的钌（I）、锰（I）、钌（II）和铂（IV）配合物以及正方形平面的铂（II）配合物。本文报道了新型夹心式η-环己烯基铁（II）TriP配合物的合成、表征及其氧化还原行为。
Ferrocene, an iron(II) center sandwiched by a pair of aromatic cyclopentadienyl (Cp) ligands, is the first known and archetypal metallocene that was discovered in 1951. After that, research into ferrocene-containing compounds continues apace within diverse areas, such as redox mediator, catalyst, electron donor, rotational hinge part, and so on. However the larger macrocyclic pconjugated system with monovalent anionic character is scarcely reported so far, due to the weak coordination ability of p-extended Cp-type ligands. Especially, in poprhyin families there are a few reports in this context: (1) Cp-Sc-porphyrin, Cp-Zr-porphyrin, Cp*-Ru-porphycene (Cp* = pentamethylcyclopentadienyl), although porphyrin and porphycene are divalent ligands; (2) b,b’-fused monoruthenocenylporphyrins, bisferrocenoporphyrins, metaloporphyrcenes and cyclopentadienylruthenium p complexes of subphthalocyanines where five-membered ring part (pyrrole or cyclohexadiene moiety) acted as ligands. Only recently double-decker iron(II) complexes of dithiaethyneporphyrin and N-fused porphyrin (NFP), where they behaved as macrocyclic tridentate ligands with a single negative charge, have been reported. During the synthesis of NFP complex, they detected the Cp-Fe-NFP compound by mass spectroscopy, which has yet to be isolated. To date, the synthesis of Cp-Fe-porphyrin sandwich compound remains a considerable challenge. In 2008, we reported a facile protocol to synthesize [14]triphyrin(2.1.1) (TriP, 1) as the first example of boron-free ring contracted porphyrins. In contrast to the reported dome-shaped boron subporphyrin complexes, these novel porphyrinoids opened up the way to a previously unexplored region of contracted porphyrinoid coordination chemistry as a mono-anionic cyclic tridentate ligand. Due to the flexibility of the macrocycle, TriP has realized octahedral rhenium(I), manganese(I), ruthenium(II), and platinum(IV) complexes and square-planar platinum(II) complexes. Now we report herein the synthesis, characterization and redox behavior of novel sandwich η-cyclopentadienyl-iron(II) TriP complexes.