1,1,1,3,3,3-hexamethyltrisilane | 5089-32-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,1,1,3,3,3-hexamethyltrisilane
• 英文别名: Trimethyl(trimethylsilylsilyl)silane；trimethyl(trimethylsilylsilyl)silane
• CAS: 5089-32-7
• 化学式: C₆H₂₀Si₃
• 分子量: 176.481
• InChiKey: OFFVKJINHUQURH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.82
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,1,1,3,3,3-hexamethyltrisilane 以3%的产率得到
  参考文献：
  名称：

  MO, SIU-HONG;HOLTEN, J. D. ,, III;KONIECZNY, S.;MA, E. C. -I.;GASPAR, P. +, J. AMER. CHEM. SOC., 1982, 104, N 5, 1424-1426

  摘要：

  DOI：
• 作为产物：
  描述：

  三甲基硅烷 在 硅烷 作用下， 生成 1,1,1,3,3,3-hexamethyltrisilane
  参考文献：
  名称：

  Chemistry of atomic silicon. III. Reactions of electron bombardment produced silicon vapor with silanes

  摘要：

  DOI：

  10.1021/ja00770a046
• 作为试剂：
  描述：

  2-氨基-3-甲基-5-溴吡啶 在 三乙基硅烷 、 正丁基锂 、 偶氮二异丁腈 、 1,1,1,3,3,3-hexamethyltrisilane 、 三氟化硼乙醚 、 四丁基氟化铵 、 三溴化硼 、 N,N-二异丙基乙胺 、 zinc(II) iodide 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 50.5h， 生成 3-methyl-2-[N-(phenoxyacetyl)amino]-5-{5'-O-[(4,4'-dimethoxytriphenyl)methyl]-2'-deoxy-β-D-ribofuranosyl}pyridine-3'-O-(2-cyanoethyl-N,N-diisopropyl)phosphoramidite
  参考文献：
  名称：

  5-Substituted 2-Aminopyridine C-Nucleosides as Protonated Cytidine Equivalents:  Increasing Efficiency and Selectivity in DNA Triple-Helix Formation

  摘要：

  The easily accessible C-nucleoside 2-amino-5-(2'-deoxy-beta-D-ribofuranosyl)py (P) and its 3-methyl (P-Me) and 2'-O-methyl (P-OMe) derivatives were synthesized and incorporated as protonated cytidine equivalents in homopyrimidine oligodeoxynucleotides. T-m measurements indicate that oligonucleotides containing P or P-Me have a higher affinity to double-stranded DNA over the pH range of 6-8 than, 5-methylcytidine (C-Me) containing oligonucleotides. This increase in stability is most pronounced above pH 7.0. The average increase in T-m/modification for the dissociation of oligonucleotide d((TTTTTPTPTPTPTPT)-P-Me-P-Me-P-Me-P-Me-P-Me) from a 21-mer target duplex at pH 7.5 is 2.3 degrees C relative to oligonucleotide. d((TTTTTCTCTCTCTCT)-C-Me-C-Me-C-Me-C-Me-C-Me). The pH dependence and sequence composition effects are much less pronounced for P-Me (and also P) containing oligonucleotides than for C-Me containing ones. While oligonucleotide d((TTTCCCCTTTTCTTT)-C-Me-C-Me-C-Me-C-Me-C-Me) shows no longer any affinity to the target duplex above pH 6.5, oligonucleotide d((TTTPPPPTTTTPTTT)-P-Me-P-Me-P-Me-P-Me-P-Me) displays preserved binding with a T-m of 32.5 degrees C at pH 7.0 and even binds with a T-m of 23.3 degrees C at pH 8.0. Oligonucleotides containing P-OMe show distinctly less stable triple helices. The average decrease in T-m/modification for oligonucleotide d(TTTPTPOMeTPOMeTPOMeTPOMeTPOMeT) at pH 6.5 is 6.7 degrees C relative to the C-Me containing oligonucleotide. DNase I footprint titration experiments indicate that d((TTTTTPTPTPTPTPT)-P-Me-P-Me-P-Me-P-Me-P-Me) binds not only five times stronger to a 229 base pair DNA fragment than d((TTTTTCTCTCTCTCT)-C-Me-C-Me-C-Me-C-Me-C-Me) but also with higher selectivity; UV-melting experiments show that duplexes of d(TTTTTCTXTCTCTCT) (where X = P, P-Me, or P-OMe) With their antiparallel Watson-Crick complement are dramatically less stable (Delta T-m < -12 degrees C) at pH 8.0 than the corresponding natural duplex. Thus the new bases P and P-Me show Hoogsteen specific pairing behavior.

  DOI：

  10.1021/ja9704904

文献信息

• Synthesis and Characterization of Scandium Silyl Complexes of the Type Cp*₂ScSiHRR‘. σ-Bond Metathesis Reactions and Catalytic Dehydrogenative Silation of Hydrocarbons
  作者：Aaron D. Sadow、T. Don Tilley

  DOI：10.1021/ja040141r

  日期：2005.1.1

  The scandium dihydrosilyl complexes Cp*(2)ScSiH(2)R (R = Mes (4), Trip (5), SiPh(3) (6), Si(SiMe(3))(3) (7); Mes = 2,4,6-Me(3)C(6)H(2), Trip = 2,4,6-(i)()Pr(3)C(6)H(2)) and Cp*(2)ScSiH(SiMe(3))(2) (8) were synthesized by addition of the appropriate hydrosilane to Cp*(2)ScMe (1). Studies of these complexes in the context of hydrocarbon activation led to discovery of catalytic processes for the dehydrogenative

  钪二氢甲硅烷基配合物 Cp*(2)ScSiH(2)R (R = Mes (4), Trip (5), SiPh(3) (6), Si(SiMe(3))(3) (7); Mes = 2,4,6-Me(3)C(6)H(2), Trip = 2,4,6-(i)()Pr(3)C(6)H(2)) 和 Cp*( 2)ScSiH(SiMe(3))(2) (8) 是通过向 Cp*(2)ScMe (1) 添加适当的氢硅烷来合成的。在碳氢化合物活化的背景下对这些复合物的研究导致发现了通过 sigma-bond 复分解用 Ph(2)SiH(2) 对碳氢化合物（包括甲烷、异丁烯和环丙烷）进行脱氢硅烷化的催化过程。
• Diadamantylsilylene and its stereochemistry of addition
  作者：Dong Ho Pae、Manchao Xiao、Michael Y. Chiang、Peter P. Gaspar

  DOI：10.1021/ja00004a031

  日期：1991.2

  respectively. The siliranes are precursors for the efficient thermal and photochemical generation of diadamantylsilylene (Ad 2 Si:). The addition of thermally generated Ad 2 Si: to cis- and trans-2-butene and -3-hexene is totally stereospecific, implying reaction from a singlet electronic state of the silylene. Photoiosomerization of cis- and trans-1,1-diadamantylsiliranes complicates the study of the

  在烯烃和炔烃的存在下，通过双金刚烷基二碘硅烷的超声辐照辅助锂诱导脱卤，分别导致 1,1-二金刚烷基硅烷和 1,1-二金刚烷基硅烷的高产率。硅烷是有效热和光化学生成二金刚烷基亚甲硅烷 (Ad 2 Si:) 的前体。将热生成的 Ad 2 Si: 添加到顺式和反式 2-丁烯和 -3-己烯中是完全立体定向的，这意味着从亚甲硅烷的单线态电子状态开始反应。顺式和反式 1,1-二金刚烷基硅烷的光异构化使添加上光 Ad 2 Si 的立体化学研究复杂化，但再次观察到高度的立体特异性
• Preparation of oligosilanes containing perhalogenated silyl groups and their hydrogenation by stannanes
  作者：U. Herzog、G. Roewer

  DOI：10.1016/s0022-328x(97)00323-9

  日期：1997.10

  SiX3-SiXiMe3−i (i = 0, 1, 2; X = Cl, Br), trisilanes SiX2(SiXiMe3−i) (i = 0, 1) and branched tetrasilanes SiX(SiXMe2)3 were synthesized and their behavior towards the Lewis-base catalyzed hydrogenation by stannanes was investigated. In the case of methylchlorodisilanes SiCl3-SiCliMe3−i Si-Si bond cleavage competes with the hydrogenation reaction.

  从methylphenylsubstituted低聚的乙硅烷起始的SiX 3 -SiX我我3-我（我= 0，1，2; X =氯，溴），三硅烷的SiX 2（SIX我我3-我）（我= 0，1）和合成了支链四硅烷SiX（SiXMe 2）3，研究了它们对锡烷对路易斯碱催化加氢反应的行为。在methylchlorodisilanes的SiCl的情况下3 -SiCl我我3-我与氢化反应的Si-Si键裂解竞争。
• Photolysis of tris(trimethylsilyl)silane: trapping of sisyl radicals
  作者：Mustafa Mohamed、Michael A Brook

  DOI：10.1139/v00-085

  日期：2000.11.1

  The photolysis of tris(trimethylsilyl)silane (TTMSS) was studied in the absence and in the presence of added trapping agents such as alkenes and alcohols. It was found that, unlike the case with pyrolysis, silyl radicals rather than silylenes are produced. They may be efficiently trapped with alkenes, to give the hydrosilylation products, but not with alcohols. The major product from the photolysis

  在不存在和存在添加的捕集剂（如烯烃和醇）的情况下研究了三（三甲基甲硅烷基）硅烷 (TTMSS) 的光解。发现与热解的情况不同，产生的是甲硅烷基自由基而不是甲硅烷基。它们可以被烯烃有效地捕获，得到氢化硅烷化产物，但不能被醇捕获。在不添加捕集剂（或使用醇作为捕集剂）的情况下，TTMSS 光解的主要产物是四（三甲基甲硅烷基）硅烷。介绍了解释光产物的可能机制。关键词：氢硅烷，光解，亚甲硅烷，甲硅烷基自由基，甲硅烷基氢化物。
• Cationic Hafnium Silyl Complexes and Their Enhanced Reactivity in σ-Bond Metathesis Processes with Si−H and C−H Bonds
  作者：Aaron D. Sadow、T. Don Tilley

  DOI：10.1021/ja030024g

  日期：2003.8.1

  unidentified hafnium-containing species. However, reactions of Cp2Hf(SiR3)Me (SiR3 = Si(SiMe3)3 (8), SitBuPh2 (9), SiPh3 (10)) with B(C6F5)3 quantitatively produced the corresponding cationic hafnium silyl complexes 12-14. The complex Cp2Hf(SitBuPh2)(mu-Me)B(C6F5)3 (13) was isolated by crystallization from toluene at -30 degrees C and fully characterized, and its spectroscopic properties and crystal structure

  混合环甲硅烷基甲基络合物 CpCp*Hf[Si(SiMe3)3]Me (4) 与 B(C6F5)3 在溴苯-d5 中反应生成两性离子铪甲硅烷基络合物 [CpCpHfSi(SiMe3)3][MeB(C6F5) )3] (7)，在溶液中至少稳定 12 小时。将 PhSiH3 添加到 7 中可快速生成 HSi(SiMe3)3、CpCp*HfH(mu-H)B(C6F5)3 和低聚硅烷产品。CpCp*Hf(SiR3)Me (SiR3 = SitBuPh2, SiHMes2) 与 B(C6F5)3 的反应迅速产生定量产率的 HSiR3 以及未知的含铪物种。然而，Cp2Hf(SiR3)Me (SiR3 = Si(SiMe3)3 (8), SitBuPh2 (9), SiPh3 (10)) 与 B(C6F5)3 的反应定量地产生了相应的阳离子铪甲硅烷基配合物 12-14。复合物 Cp2Hf(SitBuPh2)(mu-Me)B(C6F5)3