HSSi(t-Bu)3 | 155645-40-2

• 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: HSSi(t-Bu)3
• 英文别名: tBu3SiSH；Tri-tert-butylsilanethiol；tritert-butyl(sulfanyl)silane
• CAS: 155645-40-2
• 化学式: C₁₂H₂₈SSi
• 分子量: 232.506
• InChiKey: QLXKSRMVXQTHQO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.26
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [Fe{N(SiMe3)2}2]2 、 HSSi(t-Bu)3 以 苯 为溶剂， 以86%的产率得到[((t)Bu3SiS)Fe]2(μ-SSi(t)Bu3)2
  参考文献：
  名称：

  亚铁轮，椭圆形[[tBu3SiS）FeX] n和立方体[[tBu3SiS）Fe（CCSitBu3）] 4。

  摘要：

  DOI：

  10.1002/anie.200351143
• 作为产物：
  描述：

  1,1,1,3,3,3-hexa-tert-butyltrisilane 在 sulfur 作用下， 以 氘代苯 为溶剂， 生成 HSSi(t-Bu)3
  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
• 作为试剂：
  描述：

  methyl 4-deoxy-2,3-O-isopropylidene-α-L-threo-pentopyranoside 在 2,3,5-三甲基吡啶 、 2,2-双(过氧化叔丁基)丁烷 、 HSSi(t-Bu)3 作用下， 以 正辛烷 为溶剂， 反应 2.5h， 以100%的产率得到methyl 4-deoxy-2,3-O-isopropylidene-β-D-erythro-pentopyranoside
  参考文献：
  名称：

  极性反转催化1,2-二醇的反热动力学自由基链差向异构化策略

  摘要：

  已应用通过硫醇进行的极性反转催化来提供一种有效的方法，用于通过在自由基链条件下将它们的丙酮化物差向异构化，将适当的1,2-二醇转化为含量较低或类似的非对映异构体。

  DOI：

  10.1016/s0040-4039(00)01502-1

文献信息

• Aggregation of [(<i>^t</i>Bu₃SiS)MX]:  Structures of {[Br₂Fe(μ-SSi<i>^t</i>Bu₃)₂FeBr(THF)]Na(THF)₄}_∞, <i>cis</i>-[(THF)FeI]₂(μ-SSi<i>^t</i>Bu₃)₂, [(<i>^t</i>Bu₃SiS)Fe]₂(μ-SSi<i>^t</i>Bu₃)₂, and Comparative Structure and Magnetism Studies of [(<i>^t</i>Bu₃SiS)MX]<i>_n</i> (M = Fe, Co, X = Cl, <i>n</i> = 12; M = Fe, Ni, X = Br, <i>n</i> = 12; M = Fe, X = I, <i>n</i> = 14)
  作者：Orson L. Sydora、Thomas P. Henry、Peter T. Wolczanski、Emil B. Lobkovsky、Evan Rumberger、David N. Hendrickson

  DOI：10.1021/ic051289u

  日期：2006.1.1

  convenient synthesis of (t)Bu(3)SiSH and (t)Bu(3)SiSNa(THF)(x)() led to the exploration of "(t)Bu(3)SiSMX" aggregation. The dimer, [((t)Bu(3)SiS)Fe](2)(mu-SSi(t)Bu(3))(2) (1(2)), was formed from [(Me(3)Si)(2)N}Fe](2)(mu-N(SiMe(3))(2))(2) and the thiol, and its dissolution in THF generated ((t)Bu(3)SiS)(2)Fe(THF)(2) (1-(THF)(2)). Metathetical procedures with the thiolate yielded aggregate precursors [X(2)

  （t）Bu（3）SiSH和（t）Bu（3）SiSNa（THF）（x）（）的方便合成导致探索“（t）Bu（3）SiSMX”聚集。二聚体[[（（t）Bu（3）SiS）Fe]（2）（mu-SSi（t）Bu（3））（2）（1（2））由[（Me（3 ）Si）（2）N} Fe]（2）（mu-N（SiMe（3））（2））（2）和硫醇及其在THF中的溶解生成（（t）Bu（3）SiS） （2）Fe（THF）（2）（1-（THF）（2））。硫醇盐的复分解过程产生聚集的前体[X（2）Fe]（mu-SSi（t）Bu（3））（2）[FeX（THF）] Na（THF）（4）（3-X，X = Cl，Br）和顺式-[（THF）IFe]（2）（mu-SSi（t）Bu（3））（2）（4）。3-Cl，3-Br和4的热脱溶剂作用提供了分子轮[Fe（mu-X）（mu-SSi（t）Bu（3））]（12）（C（6）H（6））（n ）（5-FeX，X
• Hoernig, Andreas; Rietmann, Christian; Englert, Ulli, Chemische Berichte, 1993, vol. 126, # 12, p. 2609 - 2618
  作者：Hoernig, Andreas、Rietmann, Christian、Englert, Ulli、Wagner, Trixie、Koelle, Ulrich

  DOI：——

  日期：——
• Wiberg, Nils; Kuehnel, Edwin; Schurz, Klaus, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1988, vol. 43, # 9, p. 1075 - 1086
  作者：Wiberg, Nils、Kuehnel, Edwin、Schurz, Klaus、Borrmann, Horst、Simon, Arndt

  DOI：——

  日期：——
• Ferrous Wheels, Ellipse [(tBu3SiS)FeX]n, and Cube [(tBu3SiS)Fe(CCSitBu3)]4
  作者：Orson L. Sydora、Peter T. Wolczanski、Emil B. Lobkovsky

  DOI：10.1002/anie.200351143

  日期：2003.6.16
• 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.