Synthesis and Properties of Organocobalt(III)octaethylporphyrins
Synthesis and Properties of Organocobalt(III)octaethylporphyrins
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有机钴(III)八乙基卟啉的合成与性质
DOI：
10.1246/bcsj.49.2529
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发表时间：
1976
影响因子：
4
通讯作者：
Z. Yoshida
中科院分区：
文献类型：
--
作者：
H. Ogoshi;E. Watanabe;Norihisa Koketsu;Z. Yoshida
报道了通过钴（I）配合物对不饱和化合物的亲核进攻来合成烷基钴（III）八乙基卟啉（OEP）。带有吸电子基团的烯烃和乙炔与Co（I）（OEP）反应，而带有供电子基团的烯烃如丙烯和环己烯则不反应。由Co（I）（OEP）引发的环丙基甲基酮的一种新型开环反应生成了烷基Co（III）（OEP）。乙酸钴（II）N - 甲基八乙基卟啉的还原导致分子内甲基从氮迁移到中心钴原子。根据分析、红外和核磁共振数据，确定了有机钴（III）（OEP）配合物为五配位。根据四极弛豫和钴离子的电负性，讨论了它们核磁共振谱中α - 碳原子质子信号的一些异常行为。
The syntheses of alkylcobalt(III)octaethylporphyrins(OEP) via nucleophilic attack of the Co(I) complex to unsaturated compounds are reported. Olefins with an electron-withdrawing group and acetylenes react with Co(I)(OEP), whereas olefins with an electron-donating group such as propylene and cyclohexene are unreactive. A novel ring cleavage of cyclopropyl methy ketone initiated by Co(I)(OEP) affords alkylCo(III)(OEP). The reduction of cobalt(II) N-methyloctaethylporphyrin acetate results in intramolecular methyl migration from nitrogen to the central cobalt atom. Five-coordination has been established for the organocobalt(III)(OEP) complexes on the basis of their analytical, infrared and NMR data. Some anomalous behavior of the proton signals of the α-carbon atom in their NMR spectra has been discussed in terms of quadrupolar relaxation and electronegativity of the cobalt ion.