Research on the Synthesis and Properties of Polysilanes Containing Conjugated Si-Si Double Bonds

含共轭Si-Si双键聚硅烷的合成及性能研究

基本信息

批准号：
01470019
负责人：
MATSUMOTO Hideyuki
金额：
$ 4.1万
依托单位：
Gunma University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

项目摘要

(a) Condensation of 1, 1, 1-tribormo-2, 2, 2-triethyldisilane with sodium afforded ploy (triethylsilylsilyne) (1) in 70% yield. Gel permeation chromatography of 1 indicated a Mw=1400 versus polystyrene,in a single envelope with polydispersity of 1.04. Characterization was achieved by ^<29>Si, ^<13>C, and ^1H NMR spectrocopy, and infrared spectrocopy. The ^<29>Si NMR spectrum of 1 exhibited broad resonance centered at +150 ppm, which was assigned to the sp^2 Si atoms of the oligomer backbone.(b) Electrochemical properties of iodine-doped sample of 1 was measured. The completely doped sample was obtained as black precipitate from the dichloromethane solution of 1 and iodine.The sample showed a metallic behavior, first observed for organosilicon compounds, above 170 K and became semiconducting eith an activation energy, Ea, of 0.3 meV.(c) Novel unsaturated cyclopolysilanes such as tetrasilacyclobutene and octasilacycloocta-1, 5-diene were generated photochemically from dodecaisopropyltricyclo [4.2.0.0^<2, 5>] octasilane (2). When a solution of 2 and methanol in cyclohexane was irradiated for 3 min at room temperature, with a high-pressure mercury lamp, 2 was cleanly photoalyzed to give 1-methoxy-1, 2, 3, 3, 4, 4-hexaisopropylcyclotetrasilane exclusively. The formation of the cycloterasilane is indicative of the formation of a tetetrasilacyclobutene intermediate, which could be trapped by methanol. Similar photolysis of the syn isomer was found to afford lead a dodecaisopropyloctasilacycloocta-1, 5-diene intermediate, which could be trapped by methanol.

（a）1、1、1-1- tribormo-2、2、2-三乙烷与钠的凝结可得到70％的收率。 1的凝胶渗透色谱法表示MW = 1400与聚苯乙烯，在单个包膜中，多分散性为1.04。通过 ^<29> Si， ^<13> C和 ^1H NMR光谱和红外光谱来实现表征。 1个以+150 ppm为中心的 ^<29> Si NMR光谱表现出宽阔的共振，该共振被分配给寡聚骨架的sp ^2 Si原子。从1和碘的二氯甲烷溶液中获得了完全掺杂的样品。是从十二烷丙基三环的光化学生成[4.2.0.0^<2，5>] octasilane（2）。当在室温下将2和甲醇的2和甲醇的溶液辐照3分钟，并带有高压汞灯，将2个清晰光化的液化为1-甲氧基-1、2、2、3、3、4、4-羟基甲丙基环甲基环甲基甲烷。环脉硅烷的形成表明形成四乙烯环丁烯中间体，可能被甲醇捕获。发现同性异构体的类似光解会带来铅的二十二烷二乙烯氯乙烯和5-二烯中间体，该中间体可能被甲醇捕获。