Preparation of a diethynyl hypervalent silicon monomer by coordination-selective cleavage: structure and polymerization to give novel polycarbosilanes containing main-chain hexacoordinate silicon
作者:Karine Boyer-Elma、Francis H. Carré、Robert J.-P. Corriu、William E. Douglas
DOI:10.1039/c39950000725
日期:——
The hexacoordinate monomer R2Si(CCH)2[R = 8-(dimethylamino)naphthyl; the X-ray crystal structure showing both nitrogens trans to the ethynyl groups], formed from R2Si(CCSiMe3)2 by coordination-selective cleavage of the trimethylsilyl–acetylene bonds in the presence of Bun4NF, undergoes palladium-catalysed cross-coupling polymerization with dihaloarenes to afford novel polycarbosilanes [R2SiCCArCC]n(Ar = 1,4-pnenylene, 4,4′-biphenylene, 9,10-anthrylene) containing hexacoordinate silicon.
六配位单体 R2Si(CCH)2[R = 8-(二甲基氨基)萘基;X 射线晶体结构显示两个硝基都反式连接到乙炔基上],由 R2Si(CCSiMe3)2,在 Bun4NF 的存在下,通过配位选择性裂解三甲基硅烷基-乙炔键而形成、在钯催化下与二卤代烯烃发生交叉偶联聚合反应,生成含有六配位硅的新型聚碳硅烷 [R2SiCCArCC]n(Ar = 1,4-烯烃、4,4′-联苯、9,10-蒽)。