Studies on Synthesis and Properties of Molecular Crystalline Organopolysilanes

1.制备了反、反、反十六烷基异丙基五环[6.4.0.0^<2,7>.0^<3,6>.0^<9,12>]-十二烷基硅烷，并用x射线晶体学对其结构进行了表征。梯形聚硅烷的两条线性六硅烷链单向旋紧，且分子具有部分双螺旋结构；螺旋结构是由折叠的环四硅烷环上下交替连接的系统链交作用形成的。由K还原生成的五环阴离子自由基在室温下持续数月；一个月后ESR信号的强度损失为19%，半衰期太长，无法测量。这种显著的稳定性是前所未有的聚硅烷阴离子自由基。2.二价钯PdCl_2 (PhCN) _2_2与十异丙基双环[2.2.0]己硅烷反应生成1,4-二氯十异丙基双环己硅烷。3.十异丙基双氯的处理[2.2…更多][0]六硅烷与MCPBA氧化得到十异丙基-7-恶沙环-[2.2.1]七烷和十异丙基-2-恶沙环[3.2.0]-七烷作为单氧化产物。由于氧原子的n轨道与Si-Si sigma键的相互作用，7-oxa化合物在紫外光谱中表现出不同寻常的性质。该化合物还显示出比双环己硅烷强得多的荧光。4.用PdCl_2 (PhCN) _2与反十二异丙基三环[4.2.0.0^<2,5>]辛烷开环反应，得到了新的双环体系十二异丙基双环[3.3.0]辛烷和十二异丙基双环[4.2.0]辛烷。5.辛氧辛氧辛烷的开环卤化反应导致骨架重排，同时形成立体异构体4,8-二卤辛氧辛烷-[3.3.0.0^<2,7>.0^<3,6>]辛烷。金属钠与4,8-二卤四环环十二烷的还原脱卤化反应导致了不寻常的骨架重排，形成了八环十二烷。6.八氧基-立方烷与二甲基亚砜的光氧化反应生成了新的多面体体系，八氧基-均立方烷-八氧基五环[4.3.0.0^<2,5>.0^<3,8>.0^<4,7>]-9-草氧基硅烷和二氧基八氧基-八氧基五环- 5.3.0.0^<2,6>.0^<3,9>.0^<4,8>]-5,10-二氧基二氧基五环硅烷。7.二叔丁基二氯硅烷与锂反应生成七叔丁基环四硅烷和反式-1,1,2,3,3,4-六叔丁基环四硅烷。少

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