Forging a Cage into a Chain:Stepwise Transformation of P_(4) by Silylenes to a Si_(3)P_(4) Motif

作     者：Xiaofei Sun Alexander Hinz Peter W.Roesky 

作者机构：Institute of Inorganic ChemistryKarlsruhe Institute of Technology(KIT)76131 Karlsruhe 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2022年第4卷第6期

页      面：1843-1849页

学科分类：07[理学] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the Deutsche Forschungsgemeinschaft(DFG)[project no.470309834(Ro2008/21-1 and HI 2063/1-1)] the support by the state of Baden-Württemberg through bwHPC and DFG[grant no.INST 40/467-1 FUGG(JUSTUS cluster)]. 

主　　题：phosphorus P_(4)activation silylene silicon main group synthesis 

摘      要：We have discovered a route to access the longest low-valent molecular silaphospha-chain,a sevenmembered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phosphorus(P_(4))using two different silylene precursors.The chain species was formed via a highly reactive polyphosphide intermediate.The isolation of a stable analogue of this reaction intermediate was achieved by stepwise reaction with mono and bis(silylenes).Due to the rigidity of the ferrocenediyl framework of the bis(silylene),the isomerization process of the chain structure was hampered.Theoretical studies such as natural bond orbital and atoms in molecules analyses of the seven-membered chain species indicated some degree of delocalization of the double bond system.