Methyldisupersilylsilan | 283163-00-8

• 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: Methyldisupersilylsilan
• 英文别名: Tritert-butyl-[methyl(tritert-butylsilyl)silyl]silane；tritert-butyl-[methyl(tritert-butylsilyl)silyl]silane
• CAS: 283163-00-8
• 化学式: C₂₅H₅₈Si₃
• 分子量: 442.992
• InChiKey: TVTVWUVGCPZANX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  28
• 可旋转键数：
  8
• 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：

  Methyldisupersilylsilan 在 溴 作用下， 以 二氯甲烷 为溶剂， 生成 Dibrommethylsupersilylsilan
  参考文献：
  名称：

  超甲硅烷基硅烷 R * SiX3：表征、表征和结构；取代基 X [1] / 超甲硅烷基硅烷 R * SiX3 的空间和范德华效应：合成、表征和结构；取代基 X 的空间和范德华效应 [1]

  摘要：

  超甲硅烷基硅烷 R * SiX3（R * = 超甲硅烷基 = SitBu3；X = H、Me、tBu、Ph、SiMe3、F、Cl、Br、I、OMe、OSO2CF3）通过 (i) 超甲硅烷基卤硅烷与超甲硅烷基钠 NaR 反应制备（Hal / R * 交换），（ii）通过超甲硅烷基卤硅烷与氢化物 H-（Hal / H 交换）的反应，（iii）通过超甲硅烷基硅烷与卤素 Hal2 的反应（H / Hal 交换，R * / Hal 交换），（ iv) 通过超甲硅烷基硅烷与 F-、MeO- 等亲核试剂的反应（Hal / F 或 Hal / OMe 交换）和 (v) 通过超甲硅烷基硅烷与强酸的反应（H / OSO2CF3 交换）。R * SiX3 的 SiX3 基团的 NMR 化学位移 δ (29Si) 在很大程度上取决于 X 的性质。超甲硅烷基硅烷 R * SiX3 部分对湿气敏感（尤其是具有 SiX3≡

  DOI：

  10.1515/znb-2000-0509
• 作为产物：
  描述：

  2-Bromo-1,1,1,3,3,3-hexa-tert-butyl-2-methyl-trisilane 在 sodium 、 三乙胺盐酸盐 作用下， 以 正庚烷 、 苯 为溶剂， 生成 Methyldisupersilylsilan
  参考文献：
  名称：

  关于硅烷化学的新方面，特别是第一甲硅烷基二甲酸酯[K（Me2SiO）7] [（tBu3Si）2MeSi-Na-SiMe（SitBu3）2]的形成和结构

  摘要：

  ：通过三步合成法制备硅化物Na [SiMe（Si t Bu 3）2 ]：第一步，将两当量的Na [Si t Bu 3 ]与Cl 2 MeSi‐H反应，得到（t Bu 3 Si）2 MeSi–H。在第二步中，将硅烷（t Bu 3 Si）2 MeSi–H溴化。因此，我们可以分离出适合于X射线衍射的（t Bu 3 Si）2 MeSi-Br单晶（单斜晶，空间群C 2 / c）。（t的后续反应在室温下，Bu 3 Si）2 MeSi-Br与钠一起生成庚烷中的硅烷Na [SiMe（Si t Bu 3）2 ]。室温下从庚烷中生长出无施主硅烷Na [SiMe（Si t Bu 3）2 ]（单斜晶，空间群P 2 1 / c）的X射线晶体。K [O t Bu]和Na [SiMe（Si t Bu 3）2 ]的1：1溶液的29 Si NMR光谱显示出共振，这既不能归因于Na [SiMe（Si t Bu）3）2 ]或K

  DOI：

  10.1002/zaac.201800157

文献信息

• Supersilylsilane R*SiX₃: Umwandlung in Disilane R*X₂Si-SiX₂R*, Silylene R*XSi, Cyclosilane (R*XSi)_n, Disilene R*XSi=SiXR*, Tetrasupersilyl-tetrahedro-tetrasilan [1] / Supersilylsilanes R*SiX₃: Conversion into Disilanes R*X₂Si-SiX₂R*, Silylenes R*XSi, Cyclosilanes (R*XSi)_n, D isilenes R*XSi=SiXR*, Tetrasupersilyl-tetrahedro-tetrasilane [1]
  作者：Nils Wiberg、Wolfgang Niederm

  DOI：10.1515/znb-2000-0510

  日期：2000.5.1

  Supersilylmonohalosilanes R*R SiHCl (R * = Supersilyl = SitBu₃) react with Na in C₆H₆ at 65 °C or with NaC₁₀H₈ in THF at - 78 °C with formation of disupersilyldisilanes R*RHSi- SiHRR * in quantitative (R = H , Me) or moderate yields (R = Ph). In the latter case, R *PhSiH₂ is obtained additionally at 65 °C (exclusively with Na in THF at 65 °C). Obviously, the supersilylsilanides NaSiHRR* are generated as interm ediates which react with educts R *RSiHCl with NaCl elimination and formation of R*RHSi-SiHRR* (R = H , Me) or R *RSiH₂ and R *R Si (R = Ph). The silylene intermediate R*PhSi inserts into the SiH -bonds of the educt R*PhSiHCl and of the product R *PhSiH₂ with formation of the disupersilyldisilanes R*PhSiH -SiClPhR* and R*PhSiH -SiHPhR* which are reduced by Na at 65 °C to R*PhSiH₂ (and by NaC₁₀H₈ at low tem peratures to give R*PhSiH-SiHPhR*). The addition of NaR * to R*RSiHCl in THF at low temperatures leads with NaCl elimination to R*₂RSiH (R = H , Me) or to R*RHSi-SiHRR* (R = Me) besides R*C1, or to R*RHSi-SiClRR* (R = Ph) besides R*H and NaR , whereas the addition of R*PhSiH Cl to NaR* in THF at low temperatures results in the formation of NaSiPhR*₂ besides R*H and NaCl. In the latter cases (R = Ph), NaR* react with R*PhSiHCl to release the silylene R*PhSi, the transistory existence of which could be proven by trapping it with Et₃SiH (formation of R *Ph(Et₃Si)-SiH ). Subsequently, R*PhSi inserts into the SiH bond of R*PhSiH Cl (addition of NaR* to R*PhSiHCl) or into the NaSi bond of NaR * (addition of R*PhSiHCl to NaR *). - Supersilyldihalosilanes R*SiHCl₂ are converted by Mg in C₆H₆ at 65 °C into cyclosilanes (R *SiH)_n (n = 3, 4) and R*PhSiBrCl by Na at low temperatures - via the silylene R*PhSi - into the disilene R*PhSi=SiPhR*. which is reduced by excess Na to an anion radical. - Supersilyltrihalosilanes R*SiBr₂Cl, R*SiBr₃ and R*SiI₃ react with Na, NaC₁₀H₈ or NaR* in T H F with formation of tetrasupersilyl-terrahedro-tetrasilane (R*Si)₄ in quantitative yields, whereas the reactions of R*SiCl₃ with LiC₁₀H₈ in THF at 45 °C lead to (R*Si)₄ only in m oderate yields. Obviously, the tetrahedrane is formed from R*SiHal₃ via R*SiHal₂Na and R*HalSi=SiHalR* as reaction intermediates. The results lead to the following conclusions: (i) Silylenes play a rôle in dehalogenation of “sterically overloaded" supersilylhalosilanes R*R_3-nSiHal_n· - (ii) A straight-forward procedure for a high-yield synthesis of (R *Si)₄ from easily available educts consists in supersilanidation of SiH₂Cl₂ with NaR*, bromination of the formed supersilylsilane R*SiH₂Cl with Br₂ and dehalogenation of the bromination product R*SiBr₂Cl with Na.

  Supersilylmonohalosilanes R*R SiHCl（R* = Supersilyl = SitBu3）在65°C下与C6H6中的Na反应，或者在-78°C下与THF中的NaC10H8反应，形成双超硅基二硅烷R*RHSi-SiHRR*，其产率为定量（R = H，Me）或中等产率（R = Ph）。在后一种情况下，还在65°C下额外获得R*PhSiH2（仅与在65°C下的THF中的Na反应）。显然，超硅基硅化物NaSiHRR*作为中间体生成，它们与反应物R*RSiHCl反应，消除NaCl并形成R*RHSi-SiHRR*（R = H，Me）或R*RSiH2以及R*R Si（R = Ph）。硅烯中间体R*PhSi插入到反应物R*PhSiHCl和产物R*PhSiH2的SiH键中，形成双超硅基二硅烷R*PhSiH -SiClPhR*和R*PhSiH -SiHPhR*，它们在65°C下被Na还原为R*PhSiH2（在低温下通过NaC10H8还原为R*PhSiH-SiHPhR*）。在低温下，将NaR*添加到THF中的R*RSiHCl中，与NaCl消除形成R*2RSiH（R = H，Me）或R*RHSi-SiHRR*（R = Me），此外还有R*C1，或者R*RHSi-SiClRR*（R = Ph）以及R*H和NaR，而将R*PhSiHCl添加到NaR*中在低温下的THF中，结果形成NaSiPhR*2，此外还有R*H和NaCl。在后一种情况下（R = Ph），NaR*与R*PhSiHCl反应释放出硅烯R*PhSi，其瞬时存在性通过用Et3SiH捕获它来证实（形成R*Ph（Et3Si）-SiH）。随后，R*PhSi插入到R*PhSiHCl的SiH键中（将NaR*添加到R*PhSiHCl）或插入到NaR*的NaSi键中（将R*PhSiHCl添加到NaR*）。超硅基二卤代硅烷R*SiHCl2在65°C下通过Mg转化为环硅烷（R*SiH）n（n = 3, 4），并且在低温下通过Na转化为R*PhSiBrCl - 通过硅烯R*PhSi - 转化为双硅烯R*PhSi=SiPhR*，过量Na还原为阴离子自由基。超硅基三卤代硅烷R*SiBr2Cl、R*SiBr3和R*SiI3与Na、NaC10H8或NaR*在THF中反应，形成四超硅基四面体四硅烷（R*Si）4，产率定量，而R*SiCl3与LiC10H8在45°C下反应，只以中等产率形成（R*Si）4。显然，四面体烷是从R*SiHal3通过R*SiHal2Na和R*HalSi=SiHalR*作为反应中间体形成的。结果得出以下结论：（i）硅烯在“立体过载”的超硅基卤代硅烷R*R3-nSiHaln的脱卤作用中发挥作用；（ii）从易获得的反应物中合成（R*Si）4的高产率方法是将SiH2Cl2与NaR*进行超硅基化，用Br2对形成的超硅基硅烷R*SiH2Cl进行溴化，再用Na对溴化产物R*SiBr2Cl进行脱卤。
• Silylene R*XSi (R*=SitBu3; X=H, Me, Ph, Hal, R*): Bildung und Reaktionen
  作者：Nils Wiberg、Wolfgang Niedermayer

  DOI：10.1016/s0022-328x(01)00745-8

  日期：2001.5

  Thermolyses of disupersilylsilanes (R2SiX2)-Si-* (R* = supersilyl = (SiBu3)-Bu-t; X = H, Hal or H together with Me, Ph, Pr) at about 160 degreesC lead - besides R*X (R*H preferred to R*Br) - to silylenes R*XSi (X = H, Me, Ph, Pr), the intermediate existence of which is proven by trapping them with Et3SiH (formation of Et3Si-(R*XSi)-H), with I-2 (formation of I-(R*XSi)-I) or with CH2=CH-CH=CH2 (formation of [1+4] cycloadducts). The rate of R*X elimination increases in direction R-2*SiH2 < R-2*SiMeH < R-2*SiBrH and R-2*SiF2 < R-2*SiBr2 < R-2*SiI2. In addition, silylenes R*XSi are produced from monosupersilylsilanides R*XSiHalM (X = H, Ph, Hal; M = Na, MgHal) by MHal elimination at low temperatures and trapped by inserting them into SiH- or SiM-bonds of Et3SiH, R*PhClSiH, R*Na and R*XSiHalM. Thermolyses of R*SiX2Na (X = Cl, Pr, I) yield - via R*XSi - disilanides R*X2Si-(R*XSi)-Na which at about -20 degreesC eliminate NaX with formation of trans-configurated disilenes R*XSi=SiXR* as intermediates. In addition, R*SiCl2Na transforms into R*Cl2Si-(R*ClSi)(n)-Na (n = 2, 3) which eliminates NaCl with formation of cyclosilanes (R*ClSi)(n+1). Finally, disupersilylsilanides R-2*SiHalLi eliminate LiF at room temperature or LiCl at - 78 degreesC or LiBr at - 120 degreesC with formation of the silylene R-2*Si which stabilizes by formation of the silane R-2*SiH2 and the disilacyclobutane -R*HSi-(SiBu2)-Bu-t-CMe2-CH2- in the molar ratio 1:6. Possibly, in the latter case R-2*Si is not formed in the singulet state, as is usual with silylenes, but in the triplet state for the first time. (C) 2001 Elsevier Science B.V. All rights reserved.