Synthesis and Properties of an 18π Aromatic Norcorrole P(V) Complex
Synthesis and Properties of an 18π Aromatic Norcorrole P(V) Complex
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18π芳香族降可咯P(V)配合物的合成及性能
DOI：
10.1021/acs.orglett.1c00823
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发表时间：
2021
期刊：
影响因子：
5.2
通讯作者：
Shinokubo Hiroshi
中科院分区：
文献类型：
--
作者：
Yoshida Takuya;Shafie Siham Asyiqin;Kawashima Hiroyuki;Fukui Norihito;Shinokubo Hiroshi
[16]去甲可罗是一种反芳香环收缩的类卟啉。在这里，我们表明，磷插入的游离碱[16]norcorrole开关其反芳香性的芳香性。在吡啶溶液中用三溴化磷处理游离的间位二甲叉三甲苯基[16]去甲可咯，得到[18]去甲可咯P（V）配合物，其具有类似卟啉的吸收和荧光光谱。磷中心采用扭曲的四棱锥配位几何构型。[18]去甲可咯P（V）络合物的独特芳香性在实验和理论上都得到了证实。
[16]Norcorrole is an antiaromatic ring-contracted porphyrinoid. Here, we show that the phosphorus insertion of the free-base [16]norcorrole switches its antiaromaticity to aromaticity. The treatment of a free-basemeso-dimesityl[16]norcorrole with phosphorus tribromide in pyridine afforded an [18]norcorrole P(V) complex, which exhibited porphyrin-like absorption and fluorescence spectra. The phosphorus center adopted a distorted tetragonal pyramidal coordination geometry. The distinct aromatic nature of the [18]norcorrole P(V) complex was corroborated both experimentally and theoretically.