Yao Shenglai, Budde Markus Stefan, Yang Xing, Xiong Yun, Zhao Lili, Driess Matthias
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 115, Sekr. C2, 10623, Berlin, Germany.
State Key Laboratory of Materials-Oriented Chemical Engineering, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, 211816, China.
Angew Chem Int Ed Engl. 2025 Jan 10;64(2):e202414696. doi: 10.1002/anie.202414696. Epub 2024 Oct 31.
The facile reaction of the SiPh-bridged bis-silylene (LSi:)SiPh (L=PhC(NBu)) with diphenylacetylene affords the unprecedented 1,2,3-trisilacyclopentadiene (LSi)(PhC)SiPh 1 with a hypercoordinate λSi-λSi double bond. Compound 1 is very oxophilic and consumes three molar equivalents of inert NO to form the bicyclic oxygenation product 2 through O-atom insertion in the Si=Si and Si-Si bonds. Strikingly, 1 can completely split the C≡O bonds of carbon monoxide under ambient conditions (1 atm, room temperature), yielding the 1,3-disilacyclopentadiene 3, representing the first hypercoordinate example of a cyclosilene with a λSi-λC double bond. Likewise, reaction of Xyl-NC (Xyl=2,6-dimethylphenyl), an isocyanide isoelectronic with CO, with 1 furnishes the related 1,3-disilacyclopentadiene 4 but with an amidinato silylene pendent attached to the Si=C carbon ring atom.
硅苯基桥连双硅烯（LSi:）SiPh（L = PhC(NBu)）与二苯乙炔的简便反应得到了前所未有的1,2,3 - 三硅环戊二烯（LSi）(PhC)SiPh 1，其具有超配位的λSi-λSi双键。化合物1具有很强的亲氧性，消耗三摩尔当量的惰性NO，通过在Si = Si和Si - Si键中插入O原子形成双环氧化产物2。令人惊讶的是，1在环境条件（1个大气压，室温）下能完全裂解一氧化碳的C≡O键，生成1,3 - 二硅环戊二烯3，这是具有λSi-λC双键的环硅烯的首个超配位实例。同样，与CO等电子的异腈Xyl - NC（Xyl = 2,6 - 二甲基苯基）与1反应，得到相关的1,3 - 二硅环戊二烯4，但在Si = C碳环原子上连接有一个脒基硅烯侧基。
