Research on the Synthesis and Properties of Polysilanes Containing Conjugated Si-Si Double Bonds
Research on the Synthesis and Properties of Polysilanes Containing Conjugated Si-Si Double Bonds
批准号:
01470019
负责人:
MATSUMOTO Hideyuki
金额:
$4.1万
依托单位:
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
项目状态:
已结题
起止时间:
1989 至 1990
中文摘要
(a)1,1,1-三硼基-2,2,2-三乙基二硅烷与钠缩合得到聚(三乙基硅基硅炔)(1),产率70%。1的凝胶渗透色谱法表明相对于聚苯乙烯,在具有1.04的多分散性的单个包封中Mw=1400。通过13 <29>Si、13 <13>C和131 H NMR光谱和红外光谱进行表征。1<29>的1H Si NMR谱显示出以+150 ppm为中心的宽共振,这被归属于低聚物主链的sp^2 Si原子。(b)测试了碘掺杂样品的电化学性能。完全掺杂的样品从1和碘的二氯甲烷溶液中得到黑色沉淀,样品在170 K以上显示出金属行为,这是首次在有机硅化合物中观察到的,并且变成半导体,活化能Ea为0.3 meV。(c)以十二异丙基三环[4.2.0.0 ^<2,5>]八硅烷(2)为原料,通过光化学反应合成了四硅环丁烯和八硅环辛-1,5-二烯等新型不饱和环聚硅烷.当2和甲醇在环己烷中的溶液在室温下用高压汞灯照射3 min时,2被干净地光解,仅得到1-甲氧基-1,2,3,3,4,4-六异丙基环四硅烷。环四硅烷的形成表明四硅杂环丁烯中间体的形成,其可以被甲醇捕获。发现顺式异构体的类似光解提供铅十二异丙基辛硅环辛-1,5-二烯中间体,其可被甲醇捕获。
英文摘要
(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.
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H.Matsumoto: "The First Octasilacubane System:Synthesis of Octakis(t-butyldimethylsilyl)pentacyclo〕4.2.0.0^<2,5>.0^<3,8>.0^<4,7>〕-octasilane" J.Chem.Soc.Chem.commun.1083-1084 (1988)
H.Matsumoto:“第一个 Octasilacubane 系统:Octakis(叔丁基二甲基甲硅烷基)五环]4.2.0.0^<2,5>.0^<3,8>.0^<4,7>]-八硅烷的合成” J .Chem.Soc.Chem.commun.1083-1084 (1988)
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H. Shizuka, H. Matsumoto,: "Photolysis of Cyclotetra-Silanes" J. Chem. Soc., Chem. Commun.,. 2369-2379 (1989)
H. Shizuka,H. Matsumoto,“环四硅烷的光解”J. Chem。
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H.Matsumoto,Y.Yagihashi,A.Sakamoto,Y.Nagai,andM.Goto: "MolecularStructureandConformationalAnalysisofaPersilylcyclotetrasilane,Octakis(ethyldimethylsilyl)cyclotetrasilane" Chem.Left.
H.Matsumoto、Y.Yagihashi、A.Sakamoto、Y.Nagai 和 M.Goto:“紫苏基环四硅烷、Octakis(乙基二甲基甲硅烷基)环四硅烷的分子结构和构象分析” Chem.Left。
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H.Matsumoto: "Silicon-Branched Polysilanes in"New Aspects of Organic Chemistry I"(分担)" Kodansha-VCH, 565 (1989)
H.Matsumoto:“有机化学新方面 I”中的硅支化聚硅烷(分享)”讲谈社 VCH,565 (1989)
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共 18 条
Design of Three-Phase-Separable Flow Reactor Systems with Sensors for Monitoring the State of Catalytic Phase
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批准号:22560756
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$2.91万
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财政年份:2010
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负责人:MATSUMOTO Hideyuki
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依托单位:
Synthesis of Stable Silyl Radicals and Their Application to Multi-spin System
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Syntheses and Properties of Cyclopolysilanes with Well-defined Structures as Models for σ-Conjugation
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批准号:09304058
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财政年份:1997
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负责人:MATSUMOTO Hideyuki
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依托单位:
Studies on Synthesis and Properties of Molecular Crystalline Organopolysilanes
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批准号:06453034
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项目类别:Grant-in-Aid for General Scientific Research (B)
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资助金额:$4.42万
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财政年份:1994
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负责人:MATSUMOTO Hideyuki
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依托单位: