Nishinaga Tohru, Inoue Ryota, Matsuura Akira, Komatsu Koichi
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
Org Lett. 2002 Nov 14;4(23):4117-20. doi: 10.1021/ol026841n.
Fluorene 1 fully annelated with bicyclo[2.2.2]octene units was newly synthesized and oxidized to stable cationic species. The structure of radical cation salt 1(.+)SbCl(6)(-) was determined by X-ray crystallography, while the first fluorene dication 1(2+) was characterized by (1)H and (13)C NMR at -80 degrees C. Combined with the results of theoretical calculations, an important contribution of a quinoidal structure to the resonance hybrid was demonstrated in both 1(.+) and 1(2+). [structure: see text]
新合成了完全与双环[2.2.2]辛烯单元稠合的芴1，并将其氧化为稳定的阳离子物种。通过X射线晶体学确定了自由基阳离子盐1(+)SbCl(6)(-)的结构，而首个芴二价阳离子1(2+)则在-80℃下通过(1)H和(13)C NMR进行了表征。结合理论计算结果，在1(+)和1(2+)中均证明了醌式结构对共振杂化体的重要贡献。[结构：见正文]
