Yamazaki Daisuke, Nishinaga Tohru, Komatsu Koichi
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
Org Lett. 2004 Nov 11;6(23):4179-82. doi: 10.1021/ol0483605.
New dibenzothiophene 2 fully annelated with bicyclo[2.2.2]octene units was synthesized and oxidized to stable radical cation salt 2(+)SbCl(6)(-), whose structure was determined by X-ray crystallography. Although the intrinsic electronic structure of 2(+) is predicted to be close to structure A, an interaction with the counteranion makes structure B contribute significantly. A part of the salt 2(*+)SbCl(6)(-) underwent rearrangement to arenium ion 6(+), whose structure was also clarified by X-ray crystallography.
合成了与双环[2.2.2]辛烯单元完全稠合的新型二苯并噻吩2，并将其氧化为稳定的自由基阳离子盐2(+)SbCl(6)(-)，其结构通过X射线晶体学确定。尽管预测2(+)的本征电子结构接近结构A，但与抗衡阴离子的相互作用使结构B有显著贡献。盐2(*+)SbCl(6)(-)的一部分重排为芳鎓离子6(+)，其结构也通过X射线晶体学得以阐明。
