Synthesis and Characterization of the Most Distorted 16πporphyrin : 16πOctaisopropyltetraphenylporphyrin(OiPTPP)
Synthesis and Characterization of the Most Distorted 16πporphyrin : 16πOctaisopropyltetraphenylporphyrin(OiPTPP)
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最扭曲的16π卟啉的合成和表征：16π八异丙基四苯基卟啉(OiPTPP)
DOI：
10.1142/s1088424611004233
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
Y. Yamamoto
中科院分区：
文献类型：
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作者：
S. Sugawara;M. Kodama;Y. Hirata;S. Kojima;Y. Yamamoto
八异丙基四苯基卟啉(OiPTPP)是由3，4-二异丙基吡咯合成的，是一种以前未分离的不稳定杂环化合物。要提纯游离碱的18π卟啉，需要转化为其18π锌(II)络合物，层析分离和酸介导的脱金属。用SbCl5提供的无金属16π八异丙基四苯基卟啉(OiPTPP)氧化18π卟啉。X-射线结构测定表明，该新物种是迄今为止最扭曲的16π卟啉。由UV-Vis光谱监测的氧化物种的分解过程表明，引入高空间斥力对提高16π卟啉的稳定性是有效的。无金属的16πOiPTPP与LiBF_4反应，然后与Pd_2(Dba)_3反应，得到相应的18πOiPTPP钯(II)络合物，与以前报道的16π八异丁基四苯基卟啉(OiBTPP)一样。新的18π卟啉体系可以通过18πOiPTPP钯(II)络合物的X-射线分析来表征。18π金属络合物的X-射线结构也表明，与已知的18π卟啉相比，卟啉环的畸变率更大
Previously unreported octaisopropyltetraphenylporphyrin (OiPTPP) was prepared from 3,4-diisopropylpyrrole, an unstable previously unisolated heterocyclic compound. Purification of the free-base 18π porphyrin required conversion to its 18π zinc(II) complex, chromatographic separation, and acid mediated demetalation. Oxidation of the 18π porphyrin with SbCl5furnished metal-free 16π octaisopropyltetraphenylporphyrin (OiPTPP). X-ray structural determination revealed that the novel species is the most distorted 16π porphyrin to date. The time course of decomposition of the oxidized species monitored by UV-vis spectra implied that the introduction of high steric repulsion was effective for enhancing stability of the 16π porphyrin. The reaction of metal-free 16π OiPTPP with LiBF4followed by Pd2(dba)3gave the corresponding 18π OiPTPP palladium(II) complexviareduction of the OiPTPP lithium(I) complex as previously reported for 16π octaisobutyltetraphenylporphyrin (OiBTPP). The new 18π porphyrin system could be characterized by the X-ray analysis of the 18π OiPTPP palladium(II) complex. The X-ray structure of the 18π metal complex also indicated that the distortion of the porphyrin ring had become larger than that of previously known 18π porphyrins