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

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453034/
• 关键词: Molecular crystalline polysilane; Ladder polysilanes; Octasilacubane; Ladder polysilane anion radicals; Ring-opening halogenation; Oxidation; Cyclotetrasilane; 分子結晶; ポリシクロシラン; 合成

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

1.五边形梯子多硅烷，抗，抗脱甲氧二苯丙苯丙苯丙烷[6.4.0.0^<2,7> .0^.0^<3,3,6> .0^<9,12>] -dodecasilane，制备了结构，并通过X射线晶体学确定结构。梯子多硅烷螺钉的两个线性六边形链以一种方式，分子具有部分双螺旋结构。螺旋结构是由于系统的串联而导致的，即折叠环乙二醇环被上下连接。五边形的阴离子是由k的减少产生的，在室温下持续了几个月。一个月后ESR信号的强度损失为19％，半衰期时间太长而无法测量。对于多硅烷阴离子自由基，这种显着的稳定性是前所未有的。 2.与二价钯PDCL_2（PHCN）_2 _2形成1,4-二氯二氯迪克索丙基丙丙基丙烯酸甲硅烷。 3.与MCPBA的二苯丙丙基丙酰基甲基苯二甲烷的治疗[2.2…更多.0]己二硅烷可为Decaisopyl-7-oxabicyclo- [2.2.1]己二硅烷和十opropy1-2-2-氧化氢[3.2.0] -Heptasilane-Heptasilane-Hyptasilane作为单氧化产物。由于氧原子的N轨道和Si-Si Sigma键的相互作用，7-oxa化合物在紫外光谱中表现出异常的特性。该化合物的荧光也比双环己二硅烷更强。 4。抗dodcaisopyltricyclo [4.2.0.0^<2,5>] octasilane与pdcl_2（PHCN）_2的响环反应给出了新的生物学系统，即odocaisoproybicyclo [3.3.0 5。八八链酰二氧甲基苯乙烯的卤代释放卤化导致骨骼重排，并随着立体异构体的形成4,8-dihalooctathecathexyltacyclo- [3.3.0.0.0^<2,7> .0> .0> .0^.0^<3,3,3,6>] Octasilanes。与金属钠的4,8-二甲氯二氯二十二叶二氯二氯尼亚氏菌的脱盐化降低导致了异常的骨骼重排，形成了八叶核酸酯。 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^<3,3,9> .0^<4,8>] -5,10 -DioxadeCasilane。 7. Di-TERT叔丁基二氯烷与锂产生的Hepta-tertylyclotetrasilane和Trans-1,1,2,3,3,4-HEXA-HEXA-TERT-tert叔丁基甲硅烷的反应。较少的

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