Nukazawa Takumi, Iwamoto Takeaki
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan.
Chem Commun (Camb). 2021 Sep 23;57(76):9692-9695. doi: 10.1039/d1cc04332c.
1,3-Diethynylbicyclo[1.1.0]tetrasilanes that contain an unsupported bridgehead Si-Si π-bond and ethynyl π-moieties were synthesized by the reaction of a 1,3-dihalobicyclo[1.1.0]tetrasilane with the corresponding lithium acetylide. The substantial bathochromic shift of the longest-wavelength absorption band observed for the phenylethynyl-substituted bicyclo[1.1.0]tetrasilane in the solid state compared to that of the octynyl-substituted derivative suggested the presence of effective π-conjugation between the unsupported Si-Si π and ethynyl π units.
通过1,3-二卤代双环[1.1.0]四硅烷与相应的乙炔基锂反应，合成了含有未配位桥头硅-硅π键和乙炔基π部分的1,3-二乙炔基双环[1.1.0]四硅烷。与辛炔基取代衍生物相比，固态下苯基乙炔基取代的双环[1.1.0]四硅烷最长波长吸收带出现明显的红移，这表明在未配位的硅-硅π键和乙炔基π单元之间存在有效的π共轭。
