Gollner Waltraud, Renger Karin, Stueger Harald
Institute of Inorganic Chemistry, Graz University of Technology, Stremayrgasse 16, A-8010 Graz, Austria.
Inorg Chem. 2003 Jul 28;42(15):4579-84. doi: 10.1021/ic034332r.
The reaction of linear (Si(n)Cl(2)(n)(+2); n = 3-5) and cyclic (Si(5)Cl(10)) perchloropolysilanes with 1 or 2 equiv of LiN(SiMe(3))(2) results in the formation of the bis(trimethylsilyl)amino derivatives (Me(3)Si)(2)NSi(3)Cl(7) (1), (Me(3)Si)(2)NSi(4)Cl(9) (2), (Me(3)Si)(2)N(SiCl(2))(n)N(SiMe(3))(2) (n = 3, 4; n = 4, 5; n = 5, 6), cyclo-(Me(3)Si)(2)NSi(5)Cl(9) (7), and cyclo-(Me(3)Si)(2)NSi(5)Cl(8) (8). 1-8 easily can be hydrogenated with LiAlH(4) to give the corresponding amino and diamino polysilanyl hydrides. The monosubstituted and cyclic compounds 1, 2, 7, and 8 additionally afford Si-Si bond scission products, which cannot be separated in all cases. Chloro- and dichloro derivatives of Si(3)H(8), n-Si(4)H(10), and n-Si(5)H(12) are obtained from the corresponding aminosilanes and dry HCl. All compounds were characterized by standard spectroscopic techniques. For Si-H derivatives the coupled (29)Si NMR spectra were analyzed to obtain an unequivocal structural proof.
直链（Si(n)Cl(2)(n)(+2)；n = 3 - 5）和环状（Si(5)Cl(10)）全氯聚硅烷与1或2当量的LiN(SiMe(3))(2)反应，生成双（三甲基硅基）氨基衍生物（Me(3)Si)(2)NSi(3)Cl(7)（1）、(Me(3)Si)(2)NSi(4)Cl(9)（2）、(Me(3)Si)(2)N(SiCl(2))(n)N(SiMe(3))(2)（n = 3, 4；n = 4, 5；n = 5, 6）、环-（Me(3)Si)(2)NSi(5)Cl(9)（7）和环-(Me(3)Si)(2)NSi(5)Cl(8)（8）。1 - 8很容易用LiAlH(4)氢化，得到相应的氨基和二氨基聚硅烷基氢化物。单取代和环状化合物1、2、7和8还会生成Si - Si键断裂产物，在所有情况下都无法分离。由相应的氨基硅烷和干燥的HCl可得到Si(3)H(8)、正-Si(4)H(10)和正-Si(5)H(12)的氯代和二氯代衍生物。所有化合物均通过标准光谱技术进行了表征。对于Si - H衍生物，分析了耦合的(29)Si NMR光谱以获得明确的结构证据。
