tetrakis(tri-tert-butylsilyl)-tetrahedro-tetrasilane | 152389-94-1

• 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: tetrakis(tri-tert-butylsilyl)-tetrahedro-tetrasilane
• 英文别名: Tetrasupersilyl-tetrahedro-tetrasilan；Tritert-butyl-[2,3,4-tris(tritert-butylsilyl)-1,2,3,4-tetrasilatricyclo[1.1.0.02,4]butan-1-yl]silane
• CAS: 152389-94-1
• 化学式: C₄₈H₁₀₈Si₈
• 分子量: 910.07
• InChiKey: PGDNNMKDMSSGGU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.0
• 重原子数：
  56
• 可旋转键数：
  16
• 环数：
  4.0
• 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：

  tetrakis(tri-tert-butylsilyl)-tetrahedro-tetrasilane 在 水 、 碘 作用下， 生成 tetrasilyltetrahedrane-monooxide
  参考文献：
  名称：

  Disilene R *XSiSiXR*（R * = Si t Bu 3）mit siliciumgebundenen H- and Hal-Atomen X：Bildung，Isomerisierung，Reaktionen

  摘要：

  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

  DOI：

  10.1016/s0022-328x(00)00743-9
• 作为产物：
  描述：

  tetrabrom-1,2-disupersilyldisilan 在 sodium 作用下， 以 正庚烷 为溶剂， 反应 5.0h， 以52%的产率得到tetrakis(tri-tert-butylsilyl)-tetrahedro-tetrasilane
  参考文献：
  名称：

  Disilene R *XSiSiXR*（R * = Si t Bu 3）mit siliciumgebundenen H- and Hal-Atomen X：Bildung，Isomerisierung，Reaktionen

  摘要：

  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

  DOI：

  10.1016/s0022-328x(00)00743-9

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。
• Supersilylierte Disilene, Cyclotri-, Cyclotetra- sowie Tetrahedrosilane: Erzeugung, Strukturen, Bildungswege
  作者：Nils Wiberg、Christian M.M. Finger、Harald Auer、Kurt Polborn

  DOI：10.1016/0022-328x(96)06222-5

  日期：1996.8

  is not found. Mechanistic indications of the transformation of 7 into 1 came from studies of the reaction of the disilane RHBrSi-SiBrHR (3) with RNa at low temperatures, which leads to the cyclotrisilanes cis,trans-(SiHR)3 (13; 59 mol.%) and [SiHRSiHRSiR′R] (14, 5 mol.%; R′  SiH2R) as well as to the cyclotetrasilanes cis,cis,trans-, cis,trans,cis- and trans,trans,trans-(SiHR)4 (16, 17 and 18;

  为了获得有关反应2RBr机理信息2 SiSiBr 2 R（5）+ 2RNa→2RBr + 2NaBr + R 4的Si 4（1），从而导致在低温下tetrasupersilyl- tetrahedro -tetrasilane（R硅吨卜3高超甲硅烷基），5和RNa在PhCCPh的存在下发生反应，这可能是二硅烷基〉SiSi二硅烷基erSiSi的陷阱。反式-RBrSiSiBrR（7）和PhCCPh的[2 + 2]-环加合物（8）的分离证明了二烯（7）的中间存在。找不到二甲炔RSiSiR（12）和PhCCPh的环加合物。机械转变的机械指示7到1来自乙硅烷RHBrSi-SiBrHR（的反应的研究3）与RNA在低温下，这导致cyclotrisilanes顺，反- （SiHR）3（13 ; 59摩尔％）和[SiHR SiHRSiR'R]（14，5摩尔％; - [R '的SiH
• Diiodotetrasupersilylcyclotetrasilene (tBu3Si)4Si4I2—A Molecule Containing an Unsaturated Si4 Ring
  作者：Nils Wiberg、Harald Auer、Heinrich Nöth、Jörg Knizek、Kurt Polborn

  DOI：10.1002/(sici)1521-3773(19981102)37:20<2869::aid-anie2869>3.0.co;2-2

  日期：1998.11.2

  The red-orange tetrasilacyclobutene 1 (R*=SitBu3 ) is formed quantitatively by the reaction of tetrasilatetrahedrane 2 and iodine. Surprisingly, water and methanol do not react with 1 with addition to the Si-Si double bond, but instead with replacement of the silicon-bound iodine atoms with oxygen or the methoxy group, respectively. The substitutions possibly proceed by dissociative activation via

  橘红色的四硅环环丁烯1（R * = SitBu 3）是通过四硅四氢己烯2与碘反应定量形成的。令人惊讶地，除了Si-Si双键外，水和甲醇不与1反应，而是分别用氧或甲氧基代替与硅键合的碘原子。取代可能通过中间体3的解离活化而进行。
• Formation and Structure of Protonated Tetrasilatetrahedrane-monooxide, (<i>tert</i>-Bu₃Si)₄Si₄OH⁺
  作者：Masaaki Ichinohe、Nobuyuki Takahashi、Akira Sekiguchi

  DOI：10.1246/cl.1999.553

  日期：1999.7

  The reaction of tetrakis(tri-tert-butylsilyl)tetrasilatetrahedrane (1) with trityl tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB) gave protonated tetrasilatetrahedrane-monooxide, (tert-Bu3Si)4Si4OH+ (2+), whose structure was determined by X-ray crystallography.

  四(三叔丁基甲硅烷基)四硅四面体 (1) 与四[3,5-双(三氟甲基)苯基]硼酸三苯甲基酯 (TFPB) 反应得到质子化四硅四面体-单氧化物 (tert-Bu3Si)4Si4OH+ (2+)，其结构由 X 射线晶体学确定。
• A reactive Si4 cage: K(SitBu3)3Si4
  作者：Thomas M. Klapötke、Sham Kumar Vasisht、Gerd Fischer、Peter Mayer

  DOI：10.1016/j.jorganchem.2009.11.040

  日期：2010.3

  KR*Si-3(4), 2, (R* = SitBu(3)), formed by the reaction of R*Si-4(4) with 2 KC8, is an orange red solid stable at r.t. but decomposes in solution into R*Si-4(4) and a compound that reacts with excess Me3SiCl to form (Me3Si)(4)R*3ClSi8. Compound 2 is very sensitive to air and moisture. Its alcoholysis does not stabilize the protonated species HR*Si-3(4) and ends up in R*3Si3H3. Compound 2 reacts with 1/2 equivalent ICl to form a violet solid R*Si-6(8). A 1:1 reaction of 2 with SiBr4 runs differently to form ditetrahedranyl, R*Si-3(4)-Si4R*(3) which is stable at r.t. but transforms into its violet isomer R*Si-6(8) at higher temperatures. Compound 2 crystallizes as R*3Si4K(18-crown-6) and its crystal structure shows a Si-4-cage with a short Si-K linkage. It opens up at higher temperatures to acquire a unique structure in which a -CH2-CH2-group detaches itself from an ether to insert into Si-Si linkage of Si-4-unit to form a bicyclic ring. The residual chain (CH2)(10)O-6 closes itself on to a Si atom to form R*Si-3(3)(CH2-CH2)Si(C10H20O6)K(18-C-6). (C) 2009 Elsevier B.V. All rights reserved.