Preparation and Properties of Perarylated 3,4-Disila-1,5-hexadienes. A Fluorescent Disilane Accommodated in the Crystal Lattice
Preparation and Properties of Perarylated 3,4-Disila-1,5-hexadienes. A Fluorescent Disilane Accommodated in the Crystal Lattice
复制标题
DOI：
10.1021/om300551t
复制
发表时间：
2012-09
期刊：
影响因子：
2.8
通讯作者：
M. Tanabe;Ryouhei Yumoto;K. Osakada;T. Sanji;Masato Tanaka
中科院分区：
文献类型：
--
作者：
M. Tanabe;Ryouhei Yumoto;K. Osakada;T. Sanji;Masato Tanaka
由 [Ni(cod)2]、PCy3 和 H2SiPh2 制备的具有桥连甲硅烷基配体的二镍配合物 [{Ni(PCy3)}2(μ-SiHPh2)2] (1)，将 PCy3 配体与 1,2-双(二甲基膦基)乙烷 (dmpe) 进行交换，产生由两个二齿配体配位的配合物， [{Ni(dmpe)}2(μ-SiHPh2)2]。二芳基乙炔 ArC≡CAr (Ar = C6H5, C6H4OMe-4, C6H4Me-4, C6H4F-4, C6H4CF3-4, C6H4CN-4) 与 1 以 4/1 的比例进行反应，通过添加桥连甲硅烷基配体与炔烃的 Si-H 键，以及随后所得的叔甲硅烷基配体的偶联。二烯基二硅烷的 X 射线晶体学结果表明，根据乙烯基碳上的芳基，C=C-Si-Si-C=C 链具有三种构象。具有苯基取代基的乙硅烷 4a (Ar = C6H5) 包含平面 C=C–Si–Si–C=C 排列，具有较小的 Si–Si–C=C 扭转角（1.7(5) 和 6.9(5)°）。其他二烯基二硅烷 4b、c、e、f 具有更大的扭转角 (30....
A dinickel complex with bridging silyl ligands, [{Ni(PCy3)}2(μ-SiHPh2)2] (1), prepared from [Ni(cod)2], PCy3, and H2SiPh2, underwent exchange of the PCy3 ligands with 1,2-bis(dimethylphosphino)ethane (dmpe) to yield a complex coordinated by the two bidentate ligands, [{Ni(dmpe)}2(μ-SiHPh2)2]. Reactions of diarylacetylenes, ArC≡CAr (Ar = C6H5, C6H4OMe-4, C6H4Me-4, C6H4F-4, C6H4CF3-4, C6H4CN-4), with 1 in a 4/1 ratio afforded 1,2-bis{(E)-1,2-diarylethenyl}-1,1,2,2-tetraphenyldisilanes via addition of the Si–H bond of the bridging silyl ligand to the alkynes and subsequent coupling of the resulted tertiary silyl ligand. X-ray crystallography of the dialkenyldisilanes resulted in three kinds of conformation of the C═C–Si–Si–C═C chain depending on the aryl group at the vinyl carbon. The disilane with phenyl substituents, 4a (Ar = C6H5), contained a planar C═C–Si–Si–C═C alignment with small Si–Si–C═C torsion angles (1.7(5) and 6.9(5)°). The other dialkenyldisilanes, 4b,c,e,f, had much larger torsion angles (30....