1,2-disupersilyldisilan | 182567-54-0

• 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: 1,2-disupersilyldisilan
• 英文别名: Tritert-butyl(tritert-butylsilylsilylsilyl)silane；tritert-butyl(tritert-butylsilylsilylsilyl)silane
• CAS: 182567-54-0
• 化学式: C₂₄H₅₈Si₄
• 分子量: 459.067
• InChiKey: XFJWKNPTRFAKDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.93
• 重原子数：
  28
• 可旋转键数：
  9
• 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：

  1,2-disupersilyldisilan 在 溴 作用下， 以 正戊烷 为溶剂， 以100%的产率得到tetrabrom-1,2-disupersilyldisilan
  参考文献：
  名称：

  Disupersilyldisilane R * X 2 SiSiX 2 R *：Darstellung，Charakterisierung UND Strukturen; 立体效果

  摘要：

  Disupersilyldisilanes R * X 2 SiSiX 2 R *（R * = supersilyl =硅吨-Bu 3 ;中的R的情况下，两种非对映*XX'SiSiX'XR*）在有机溶剂（I），通过制备dehalogenations具有Na，NaC 10 H 8或NaR *的超甲硅烷基卤硅烷; （ii）通过用H disupersilylhalodisilanes的反应- （哈尔/ H交换）; （iii）通过二超甲硅烷基乙硅烷与Hal 2的反应（H / Hal交换）；（iv）首先使二超甲硅烷基卤代二硅烷与NaR *（Hal / Na交换），然后与用于质子化，烷基化，甲硅烷基化的试剂（Na / H，Na / Me，Na / SiMe 3交换）反应；或（v）通过二超甲硅烷基二ilenes（此处为R *PhSiSiPhR*）与HHal或Hal反应2（附加产品的形成）。如所讨论的，（29六的Si）的2的R基团*

  DOI：

  10.1016/s0022-328x(00)00442-3
• 作为产物：
  描述：

  Chlorsupersilylsilan 在 sodium 作用下， 以 苯 为溶剂， 反应 16.0h， 以71%的产率得到1,2-disupersilyldisilan
  参考文献：
  名称：

  Disupersilyldisilane R * X 2 SiSiX 2 R *：Darstellung，Charakterisierung UND Strukturen; 立体效果

  摘要：

  Disupersilyldisilanes R * X 2 SiSiX 2 R *（R * = supersilyl =硅吨-Bu 3 ;中的R的情况下，两种非对映*XX'SiSiX'XR*）在有机溶剂（I），通过制备dehalogenations具有Na，NaC 10 H 8或NaR *的超甲硅烷基卤硅烷; （ii）通过用H disupersilylhalodisilanes的反应- （哈尔/ H交换）; （iii）通过二超甲硅烷基乙硅烷与Hal 2的反应（H / Hal交换）；（iv）首先使二超甲硅烷基卤代二硅烷与NaR *（Hal / Na交换），然后与用于质子化，烷基化，甲硅烷基化的试剂（Na / H，Na / Me，Na / SiMe 3交换）反应；或（v）通过二超甲硅烷基二ilenes（此处为R *PhSiSiPhR*）与HHal或Hal反应2（附加产品的形成）。如所讨论的，（29六的Si）的2的R基团*

  DOI：

  10.1016/s0022-328x(00)00442-3

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。
• A Comparative Study of (tBu3Si)SiX2SiX2(SitBu3) (X = Cl, Br, I) Including the Result of the X-Ray Structure Analysis of (tBu3Si)SiI2SiI2(SitBu3)
  作者：Michael Bolte、Hans-Wolfram Lerner

  DOI：10.1007/s10870-010-9851-2

  日期：2011.2

  The tetraiodotetrasilane (tBu3Si)SiI2SiI2(SitBu3) can be prepared from precursor (tBu3Si)SiH2SiH2(SitBu3). When (tBu3Si)SiH2SiH2(SitBu3) was treated with an excess of iodine at 120 °C, (tBu3Si)SiI2SiI2(SitBu3) was formed. X-ray quality crystals of (tBu3Si)SiI2SiI2(SitBu3) were grown from benzene at ambient temperature. The tetraiodotetrasilane (tBu3Si)SiI2SiI2(SitBu3) crystallizes in the monoclinic space group C2/c, a = 10.0110(10) Å, b = 13.9130(10) Å, c = 25.422(2) Å, β = 99.072(4)°, V = 3496.6(5) Å3, Z = 4, d calcd = 1.829 g cm3; R 1 = 0.0844, wR 2 = 0.1854 for 3,017 reflections with I > 2σ(I). X-ray-crystallographic data show that the bromo and iodo derivatives (tBu3Si)SiX2SiX2(SitBu3) (X = Br, I) are isomorphous. The solid-state structure of (tBu3Si)SiI2SiI2(SitBu3) as well as those of (tBu3Si)SiX2SiX2(SitBu3) (X = Cl, Br) reveals a staggered conformation which adopts a trans-orientation of the supersilyl substituent. Unequal dihedral angles as found in (tBu3Si)SiX2SiX2(SitBu3) (X = Cl, Br, I) indicate that these compounds are sterically overcrowded. In the solid-state (tBu3Si)SiI2SiI2(SitBu3) features a staggered conformation which adopts a trans-orientation of the supersilyl group. However the solid-state structure of (tBu3Si)SiI2SiI2(SitBu3) reveals unequal dihedral angles.

  四碘四硅烷 (tBu3Si)SiI2SiI2(SitBu3) 可由前驱体 (tBu3Si)SiH2SiH2(SitBu3) 制备而成。在 120 ℃ 下用过量碘处理 (tBu3Si)SiH2SiH2(SitBu3) 时，会生成 (tBu3Si)SiI2SiI2(SitBu3)。(tBu3Si)SiI2SiI2(SitBu3)的 X 射线质量晶体是在环境温度下从苯中生长出来的。四碘四硅烷 (tBu3Si)SiI2SiI2(SitBu3) 在单斜空间群 C2/c 中结晶，a = 10。0110(10) Å, b = 13.9130(10) Å, c = 25.422(2) Å, β = 99.072(4)°, V = 3496.6(5) Å3, Z = 4, d calcd = 1.829 g cm3; R 1 = 0.0844, wR 2 = 0.1854 for 3,017 reflections with I > 2σ(I).X 射线晶体学数据表明，溴和碘衍生物 (tBu3Si)SiX2SiX2(SitBu3) (X = Br, I) 是同构的。(tBu3Si)SiI2SiI2(SitBu3)和(tBu3Si)SiX2SiX2(SitBu3)(X = Cl, Br)的固态结构显示出一种交错构象，超硅取代基采用了反式取向。在(tBu3Si)SiX2SiX2(SitBu3)（X = Cl、Br、I）中发现的不相等的二面角表明这些化合物在立体上过于拥挤。在固态下，(tBu3Si)SiI2SiI2(SitBu3)具有交错构象，超硅基团呈反式取向。然而，(tBu3Si)SiI2SiI2(SitBu3)的固态结构显示出不等的二面角。
• Disilene R*XSi=SiXR* (R*=SitBu3) mit siliciumgebundenen H- und Hal-Atomen X: Bildung, Isomerisierung, Reaktionen
  作者：N Wiberg

  DOI：10.1016/s0022-328x(00)00743-9

  日期：2001.1.30

  with benzophenone (formation of [2+2] cycloadducts), and/or with 2,3-dimethylbutadiene (formation of [2+2] and [4+2] cycloadducts as well as ene reaction products). Obviously, isomerization of the disilenes R*HalSiSiHalR* to silylenes R*Hal2SiSiR* is possible, the latter of which may be trapped by Et3SiH. In the absence of the mentioned traps, R*HSiSiHR* thermolizes under formation of cyclotrisilanes

  1,2- disupersilyldisilanes R *ħDehalogenations 2 SiSiHalHR*，R *HHalS​​iSiHalHR*，R *HHalS​​iSiHal 2 R *和R *哈尔2 SiSiHal 2 R *，在THF与等摩尔量supersilyl钠的NaR *（R * = Si t Bu 3 = Supersilyl）在室温下（Hal = Cl）缓慢导引，甚至在-78°C（Hal = Br，I）下也导联，而将一种卤素Hal换成钠钠则变成黄色–橙disilanides R *ħ 2 SiSiNaHR*，R *HHalS​​iSiNaHR*，R *HHalS​​iSiNaHalR*和R *哈尔2 SiSiNaHalR*（通过质子化，甲基化，甲硅烷基化识别）。然后，在后三种情况下，这些可以消除反式形成下的NaHal具有与硅键合的H和Hal原子为X的-1
• 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.