Synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes
Synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes
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DOI：
10.1351/pac-con-09-08-05
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发表时间：
2010-03-01
影响因子：
1.8
通讯作者：
Imahori, Hiroshi
中科院分区：
文献类型：
--
作者：
Matano, Yoshihiro;Nakabuchi, Takashi;Imahori, Hiroshi
综述了近年来在含磷卟啉及其金属配合物的合成、结构和芳香性等方面的研究进展。核心修饰的P，X，N-2-卟啉（X = S， N）可由sigma(4)-磷酸三吡喃和相应的2,5-二官能杂化合物在几步内得到。对sigma(3)-P，N-3卟啉的x射线结构分析表明，它具有轻微扭曲的18 π平面。核心处的磷原子对卟啉环产生前所未有的反应性和配位能力起着重要作用。P，N-3自由碱与[RhCl(CO)(2)](2)在二氯甲烷中反应，最终生成18 π P，N-3-铑（III）配合物，而P，S，N-2自由碱与零价10族金属进行氧化还原偶联络合，生成相应的P，S，N-2-异氯啉-金属（II）配合物。从实验和理论两方面揭示了游离基卟啉及其金属配合物的芳构性。特别令人感兴趣的是，P，S， n- 2-异氯啉-金属配合物在磁准则方面仅表现出弱的抗芳性。
Our recent studies on the synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes are summarized. Core-modified P,X,N-2-porphyrins (X = S, N) are accessible from a sigma(4)-phosphatripyrrane and the corresponding 2,5-difunctionalized heteroles in a few steps. X-ray structural analysis of the sigma(3)-P,N-3 porphyrin revealed that it possesses a slightly distorted 18 pi plane. The phosphorus atom incorporated at the core plays an important role in producing unprecedented reactivity and coordinating ability for the porphyrin ring. The P,N-3 free base reacts with [RhCl(CO)(2)](2) in dichloromethane, ultimately yielding an 18 pi P,N-3-rhodium(III) complex, whereas the P,S,N-2 free base undergoes redox-coupled complexation with zero valent group 10 metals to afford the corresponding P,S,N-2-isophlorin-metal(II) complexes. The aromaticity of the free-base porphyrins and the metal complexes was uncovered based on both experimental and theoretical results. It is of particular interest that the P,S,N-2-isophlorin-metal complexes exhibit only a weak antiaromaticity in terms of the magnetic criterion.