Tritert-butyl-(2,2-ditert-butyl-3,3-dimethyldisiletan-1-yl)silane | 356558-81-1

• 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: Tritert-butyl-(2,2-ditert-butyl-3,3-dimethyldisiletan-1-yl)silane
• 英文别名: tritert-butyl-(2,2-ditert-butyl-3,3-dimethyldisiletan-1-yl)silane
• CAS: 356558-81-1
• 化学式: C₂₄H₅₄Si₃
• 分子量: 426.949
• InChiKey: GFIZNEUJQUFUKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.06
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  1.0
• 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：

  Tritert-butyl-(2,2-ditert-butyl-3,3-dimethyldisiletan-1-yl)silane 在 水 、 氧气 作用下， 生成
  参考文献：
  名称：

  Silylene R*XSi (R*=SitBu3; X=H, Me, Ph, Hal, R*): Bildung und Reaktionen

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(01)00745-8
• 作为产物：
  描述：

  bis(tri-tert-butylsilyl)dichlorosilane 在 lithium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 1,1,1,3,3,3-hexa-tert-butyltrisilane 、 Tritert-butyl-(2,2-ditert-butyl-3,3-dimethyldisiletan-1-yl)silane
  参考文献：
  名称：

  Silylene R*XSi (R*=SitBu3; X=H, Me, Ph, Hal, R*): Bildung und Reaktionen

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(01)00745-8

文献信息

• Sekiguchi, Akira; Tanaka, Takashi; Ichinohe, Masaaki, Journal of the American Chemical Society, 2003, vol. 125, # 17, p. 4962 - 4963
  作者：Sekiguchi, Akira、Tanaka, Takashi、Ichinohe, Masaaki、Akiyama, Kimio、Tero-Kubota, Shozo

  DOI：——

  日期：——
• 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.