Studies on Synthesis and Properties of Molecular Crystalline Organopolysilanes

分子结晶有机聚硅烷的合成及性能研究

基本信息

批准号：
06453034
负责人：
MATSUMOTO Hideyuki
金额：
$ 4.42万
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：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

项目摘要

1.The pentacyclic ladder polysilane, anti, anti, anti-hexadecaisopropylpentacyclo [6.4.0.0^<2,7>.0^<3,6>.0^<9,12>] -dodecasilane was prepared and the structure was determined by X-ray crystallography. Two linear hexasilane chains of the ladder polysiane screw on one way, and the molecule has the partially double helical structure ; the helical structure results from the systematic catenation that the folded cyclotetrasilane rings are connected up and down alternatively. The anion radical of the pentacycle, which was generated by the reduction with K,persisted over several months at room temperature ; the intensity loss in the ESR Signal after one month is 19%, and the half-life time is too long to be measured. This remarkable stability is unprecedented for polysilane anion radicals. 2.Reaction of decaisopropylbicyclo [2.2.0] hexasilane with the divalent palladium PdCl_2 (PhCN) _2led to the formation of 1,4-dichlorodecaisopropylbicyclohexasilane. 3.Treatment of decaisopropylbicyclo [2.2 … More .0] hexasilane with MCPBA afforded decaisopropyl-7-oxabicyclo- [2.2.1] heptasilane and decaisopropy1-2-oxabicyclo [3.2.0] -heptasilane as monoxidation products. The 7-oxa compound showed unusual properties in the UV spectrum due to the interaction of the n orbital of the oxygen atom and the Si-Si sigma bonds. The compound also showed far stronger fluorescence than the bicyclohexasilane. 4.The ring-opening reaction of anti-dodcaisopropyltricyclo [4.2.0.0^<2,5>] octasilane with PdCl_2 (PhCN) _2 gave the new bicyclic systems, dodocaisoproybicyclo [3.3.0] octasilane and dodoca-isopropylbicyclo [4.2.0] octasilane. 5.The ring-opening halogenation of octathexyloctasilacubane resulted in skeletal rearrangement with concomitant formation of stereoisomeric 4,8-dihalooctathexyltetracyclo- [3.3.0.0^<2,7>.0^<3,6>] octasilanes. The reductive dehalogenation of the 4,8-dihalotracyclooctasilanes with sodium metal led to unusual skeletal rearrangement, forming the octasilacubane. 6.Photooxidation of the octasila-cubane with dimethylsulfoxide resulted in formation of the new polyhedral systems, the oxaoctasila-homocubane, octathexylpentacyclo [4.3.0.0^<2,5>.0^<3,8>.0^<4,7>] -9-oxanonasilane and the dioxaoctasilabishomo-cubane, octathexylpentacyclo [5.3.0.0^<2,6>.0^<3,9>.0^<4,8>] -5,10-dioxadecasilane. 7.The reaction of di-tert-butyl-dichlorosilane with lithium produced hepta-tert-butylcyclotetrasilane and trans-1,1,2,3,3,4-hexa-tert-butylcyclotetrasilane. Less

1.五环梯形聚硅烷，反，反，反十六异丙基五环[6.4.0.0^<2,7>.0^<3,6>.0^<9,12>]-十二硅烷的制备并确定结构通过X射线晶体学分析，梯形聚硅烷螺旋有两条直链己硅烷链，分子具有部分双螺旋结构；折叠的环四硅烷环上下交替连接的系统连接结果，由 K 还原产生的五环阴离子自由基在室温下持续数月，ESR 信号强度损失。一个月为19%，半衰期太长，无法测量。2.十异丙基双环的反应。 [2.2.0] 己硅烷与二价钯 PdCl_2 (PhCN) _2 反应生成 1,4-二氯十异丙基双环己硅烷 3. 用 MCPBA 处理十异丙基双环 [2.2 … 更多 .0] 己硅烷，得到十异丙基-7-氧杂双环- [2.2。 1]庚硅烷和十异丙基1-2-氧杂双环[3.2.0]-庚硅烷作为一氧化产物，由于氧原子的n轨道和Si-Si σ键的相互作用，7-氧杂化合物在紫外光谱中表现出不寻常的性质。 4.抗十二异丙基三环的开环反应。 [4.2.0.0^<2,5>]辛硅烷与PdCl_2(PhCN)_2反应得到新的双环体系，十二烷基异丙基双环[3.3.0]辛硅烷和十二烷基异丙基双环[4.2.0]辛硅烷5。 octathexyloctasilacubane 导致骨骼重排伴随形成立体异构体4,8-二卤代八环辛基四环-[3.3.0.0^<2,7>.0^<3,6>]八硅烷4,8-二卤代四环辛基硅烷与金属钠的还原脱卤导致不寻常的骨架重排， 6.八硅立方烷的光氧化。二甲基亚砜导致新的多面体系统的形成，即oxoctasila-homocubane、octhexylpentacyclo [4.3.0.0^<2,5>.0^<3,8>.0^<4,7>] -9-oxanonasilica和dioxaoctasilabishomo -立方烷、八烷基五环[5.3.0.0^<2,6>.0^<3,9>.0^<4,8>]-5,10-二氧十硅烷 7.二叔丁基二氯硅烷与锂反应生成庚烷。 -叔丁基环四硅烷和反式-1,1,2,3,3,4-六叔丁基环四硅烷较少。