Lithiated 1,3-Disilabicyclo[1.1.0]butanes Synthesized via Selective Cleavage of Exocyclic Si–Si Bonds on Bridgehead Silicon Atoms
作者:Takeaki Iwamoto、Dongzhu Yin、Akifumi Kobayashi、Makoto Tamura、Daiki Motomatsu、Naohiko Akasaka、Yuki Yokouchi、Shintaro Ishida、Mitsuo Kira
DOI:10.1021/acs.organomet.1c00284
日期:2021.8.9
3-di(t-butyldimethylsilyl)-1,3-disilabicyclo[1.1.0]butane 1a with excess lithium in THF provided 1,3-dilithio-1,3-disilabicyclo[1.1.0]butane 2 via reductive cleavage of the exocyclic Si–Si bonds at the bridgehead silicon atoms. In the single crystals obtained by recrystallization in the presence of 1,2-dimethoxyethane (DME), 2 exists as a solvent-separated ion pair, and its anionic part forms an aggregate
1,3-二的处理(吨丁基二)-1,3- disilabicyclo [1.1.0]丁烷1A与THF中的过量锂提供1,3-二锂-1,3- disilabicyclo [1.1.0]丁烷2经由桥头硅原子处环外Si-Si键的还原裂解。在 1,2-二甲氧基乙烷 (DME) 存在下重结晶获得的单晶中,2作为溶剂分离的离子对存在,其阴离子部分形成包含三个锂原子的聚集体,中间夹着两个 1,3-二硅杂双环[1.1.0]butan-1,3-diide 单元。用氯三异丙基硅烷处理2得到三异丙基甲硅烷基取代的 1,3-二硅杂双环 [1.1.0] 丁烷1b。1b的结构特点 接近于短键异构体,这与先前关于桥头取代基对硅杂环[1.1.0]丁烷结构的空间效应的理论预测一致。