tris(dimethylsilyl)methane | 27809-11-6

• 分子结构分类: 有机化合物
• 英文名称: tris(dimethylsilyl)methane
• 英文别名: Bis(dimethylsilyl)methyl-dimethylsilane
• CAS: 27809-11-6
• 化学式: C₇H₂₂Si₃
• 分子量: 190.508
• InChiKey: CEMZTGDTJWUTKD-UHFFFAOYSA-N

物化性质

• 沸点：
  53 °C(Press: 9 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tris(dimethylsilyl)methane 在 benzyl potassium 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以86.7%的产率得到[三(二甲基甲硅烷基)甲基]钾
  参考文献：
  名称：

  Intermolecular β-Hydrogen Abstraction in Ytterbium, Calcium, and Potassium Tris(dimethylsilyl)methyl Compounds

  摘要：

  A series of organometallic compounds containing the tris(dimethylsilyl)methyl ligand are described. The potassium carbanions KC(SiHMe2)(3) and {KC(SiHMe2)(3)-TMEDA}(2) are synthesized by deprotonation of the hydrocarbon HC(SiHMe2)(3) with potassium benzyl. {KC(SiHMe2)(3)-TMEDA}(2) crystallizes as a dimer with two types of three-center-two-electron K-H-Si interactions: side-on coordination of SiH (angle K-H-Si = 102(2)degrees) and more obtuse K-H-Si structures (angle K-H-Si approximate to 150 degrees). The divalent calcium and ytterbium compounds M{C(SiHMe2)(3)}(2)L (M = Ca, Yb; L = 2THF, TMEDA) are prepared from MI2 and 2 equiv of KC(SiHMe2)(3). Low (1)J(SiH) coupling constants in the NMR spectra, low-energy nu(SiH) bands in the IR spectra, and short M-Si distances and small M-C-Si angles in the crystal structures suggest beta-agostic interactions on each C(SiHMe2)(3) ligand. The IR assignments of M{C(SiHMe2)(3)}(2)L (L = 2THF, TMEDA) are supported by DFT calculations. The compounds M{C(SiHMe2)(3)}(2)L react with 1 or 2 equiv of B(C6F5)(3) to give the 1,3-disilacyclobutane {Me2SiC(SiHMe2)(2)}(2) and MC(SiHMe2)(3)HB(C6F5)(3)L or M{HB(C6F5)(3)}(2)L, respectively. In addition, M{C(SiHMe2)(3)}(2)L compounds react with BPh3 to give beta-H abstracted products. The compounds M{C(SiHMe2)(3)}(2)THF2 react with SiMe3I to yield Me3SiH and disilacyclobutane as the products of beta-H abstraction, while M{C(SiHMe2)(3)}(2)TMEDA and Me3SiI form a mixture of Me3SiH and the alkylation product Me3SiC(SiHMe2)(3) in a 1:3 ratio.

  DOI：

  10.1021/om3010299
• 作为产物：
  描述：

  Yb{C(SiHMe₂)₃}₂THF₂ 在 air 作用下， 以 氘代苯 为溶剂， 反应 0.01h， 生成 tris(dimethylsilyl)methane
  参考文献：
  名称：

  Intermolecular β-Hydrogen Abstraction in Ytterbium, Calcium, and Potassium Tris(dimethylsilyl)methyl Compounds

  摘要：

  A series of organometallic compounds containing the tris(dimethylsilyl)methyl ligand are described. The potassium carbanions KC(SiHMe2)(3) and {KC(SiHMe2)(3)-TMEDA}(2) are synthesized by deprotonation of the hydrocarbon HC(SiHMe2)(3) with potassium benzyl. {KC(SiHMe2)(3)-TMEDA}(2) crystallizes as a dimer with two types of three-center-two-electron K-H-Si interactions: side-on coordination of SiH (angle K-H-Si = 102(2)degrees) and more obtuse K-H-Si structures (angle K-H-Si approximate to 150 degrees). The divalent calcium and ytterbium compounds M{C(SiHMe2)(3)}(2)L (M = Ca, Yb; L = 2THF, TMEDA) are prepared from MI2 and 2 equiv of KC(SiHMe2)(3). Low (1)J(SiH) coupling constants in the NMR spectra, low-energy nu(SiH) bands in the IR spectra, and short M-Si distances and small M-C-Si angles in the crystal structures suggest beta-agostic interactions on each C(SiHMe2)(3) ligand. The IR assignments of M{C(SiHMe2)(3)}(2)L (L = 2THF, TMEDA) are supported by DFT calculations. The compounds M{C(SiHMe2)(3)}(2)L react with 1 or 2 equiv of B(C6F5)(3) to give the 1,3-disilacyclobutane {Me2SiC(SiHMe2)(2)}(2) and MC(SiHMe2)(3)HB(C6F5)(3)L or M{HB(C6F5)(3)}(2)L, respectively. In addition, M{C(SiHMe2)(3)}(2)L compounds react with BPh3 to give beta-H abstracted products. The compounds M{C(SiHMe2)(3)}(2)THF2 react with SiMe3I to yield Me3SiH and disilacyclobutane as the products of beta-H abstraction, while M{C(SiHMe2)(3)}(2)TMEDA and Me3SiI form a mixture of Me3SiH and the alkylation product Me3SiC(SiHMe2)(3) in a 1:3 ratio.

  DOI：

  10.1021/om3010299

文献信息

• Reactions of tris(dimethylsilyl)methane and polymers containing si—h groups with various hydroxy compounds under aerobic and mild conditions
  作者：Kazem D. Safa、Shahin Tofangdarzadeh、Hossein Heydari Ayenadeh

  DOI：10.1002/hc.20440

  日期：2008.5

  with styrene (in 1:1 and 1:3 mol ratio) were synthesized by free radical polymerization, and (HMe2Si)3C groups were linked to them by nucleophilic substitution reactions between (HMe2Si)3CLi and the chloromethyl groups of the polymer side chains. The resulting functional polymers containing Si—H bonds reacted with various alcohols in the presence of chloroplatinic acid under heterogeneous conditions

  三（二甲基甲硅烷基）甲烷，(HMe2Si)CH，与正丙基、异丙基、正丁基、仲丁基、异丁基、正戊基、仲戊基、正己醇和苯酚反应在空气中存在氯铂酸 (H2PtCl6ċ6H2O) 得到产物 (ROMe2Si)3CH（其中 R 是正丙基、异丙基、正丁基、仲丁基、异丁基、正戊基、仲戊基、正戊基己基、苯基）。与苯甲醇和乙酸的类似反应分别产生了意想不到的产物，(PhCH2)2O 和 HC(Me2SiOSiMe2)3CH。化合物 (n-BuOMe2Si)3CSiMe2H 由 (n-BuOMe2Si)3CH 通过用二异丙基氨基锂处理制成，然后用 HMe2SiCl 淬火。均聚物聚(4-氯甲基)苯乙烯}和与苯乙烯的共聚物（摩尔比为1:1和1:3）通过自由基聚合合成，(HMe2Si)3C 和 (HMe2Si)3C 基团通过 (HMe2Si)3CLi 和聚合物侧链的氯甲基之间的亲核取代反应与它们相连。得到的含有 Si-H
• Tridentate Lewis Acids: Boron‐, Silicon‐ and Gallium‐Functionalised Tris(dimethylsilyl)methanes
  作者：Eugen Weisheim、Anna Schwartzen、Lisa Kuhlmann、Beate Neumann、Hans‐Georg Stammler、Norbert W. Mitzel

  DOI：10.1002/ejic.201501432

  日期：2016.3

  chlorosilanes afforded flexible poly-Lewis acids equipped with B(C6F5)2, SiCl3, SiMeCl2 and SiMe2Cl substituents. The reaction of these silicon-containing tridentate Lewis acids with SbF3 led to fluorine-substituted poly-Lewis acids of the type Me3SiC[Si(Me)2CH2CH2SiMe3–nFn]3 (n = 1–3). All the compounds were characterised by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses and some by X-ray

  基于具有三个乙炔基 Me3SiC[Si(Me)2C≡C–H]3} 和三个乙烯基 Me3SiC[Si(Me)2CH=CH2]3} 的新型三甲硅烷基甲烷支架的柔性三齿路易斯酸，已经被通过用有机镓金属化合成和功能化得到 Me3SiC[Si(Me)2C≡C–GaR2]3 (R = Me, Et)。用 HB(C6F5)2 和各种氯硅烷对三甲硅烷基甲烷骨架进行加氢金属化，得到带有 B( )2、S​​iCl3、SiMeCl2 和 SiMe2Cl 取代基的柔性聚路易斯酸。这些含硅三齿路易斯酸与 SbF3 的反应产生了 Me3SiC[Si(Me)2CH2CH2SiMe3–nFn]3 (n = 1–3) 类型的氟取代的聚路易斯酸。所有化合物均通过多核 NMR 光谱、质谱、元素分析和一些 X 射线衍射进行表征。
• Synthesis of novel calix[4]arenes containing organosilicon groups
  作者：Kazem D. Safa、Yones Mosaei Oskoei

  DOI：10.1016/j.jorganchem.2009.09.021

  日期：2010.1

  olefination. The compounds (RSiMe2)3CLi were treated with 25,26,27,28-tetrakis(4-bromobutoxy)calix[4]arene (4) to give 25,26,27,28-tetrakis[4-(tris(dimethylsilyl)methyl)butoxy] calix[4]arene (5a) and 25,26,27,28-tetrakis[4-(tris(trimethylsilyl)methyl)butoxy] calix[4]arene (5b) via nucleophilic substitution reactions. However the compound 25,26,27,28-tetrakis[4-(tris(dimethylphenylsilyl)methyl)butoxy] calix[4]arene

  用二异丙基氨基锂（LDA）或甲基锂在THF中金属化（RSiMe 2）3 CH（1a R = H，1b R = Me，1c R = Ph）得到有机锂试剂（RSiMe 2）3 CLi，其与甲酰化的杯芳烃反应（2），通过如下方式得到相应的5,17-双[2,2-双（有机甲硅烷基）-1-乙烯基] -25,26,27,28-四丙氧基杯[4]芳烃（3a，3b和3c）。彼得森烯化。用25,26,27,28-四（4-溴丁氧基）杯[4]芳烃处理化合物（RSiMe 2）3 CLi（4）得到25,26,27,28-四[4-（三（二甲基甲硅烷基）甲基）丁氧基]杯[4]芳烃（5a）和25,26,27,28-四[[甲基]丁氧基]杯[4]芳烃（5b）通过亲核取代反应。但是，未得到化合物25,26,27,28-四[4-（三（二（二甲基苯基甲硅烷基）甲基）丁氧基]杯[4]芳烃（5c），这可能是因为（PhSiMe 2）3 C-
• [Tris(alkoxydimethylsilyl)methyl]alkylferrocenes as New Ferrocenyl Multifunctional Silyl Ethers
  作者：Kazem D. Safa、Hassan Abbasi、Reza Teimuri-Mofrad、Farzaneh A. Charandabi

  DOI：10.1071/ch13632

  日期：——

  [Tris(trimethylsilyl)methyl]alkylferrocenes and [tris(dimethylsilyl)methyl]alkylferrocenes were synthesized by treatment of tris(trimethylsilyl)methyllithium and tris(dimethylsilyl)methyllithium in THF with 3-bromopropylferrocene or 4-bromobutylferrocene at 0°C. [Tris(alkoxydimethylsilyl)methyl]alkylferrocenes were obtained by dehydrocoupling with various aliphatic and benzylic alcohols in the presence of the Karstedt catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene) in good to excellent yields. 4-[Tris(benzyloxydimethylsilyl)methyl]butylferrocene was also prepared from the transetherification of 4-[tris(methoxydimethylsilyl)methyl]butylferrocene with benzyl alcohol in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene as catalyst.

  三(三甲基硅烷基)甲基]烷基二茂铁和[三(二甲基硅烷基)甲基]烷基二茂铁是由三(三甲基硅烷基)甲基锂和三(二甲基硅烷基)甲基锂在 THF 中与 3-溴丙基二茂铁或 4-溴丁基二茂铁在 0°C 下处理合成的。在 Karstedt 催化剂（二甲苯中的铂(0)-1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷）存在下，通过与各种脂肪醇和苄醇进行脱氢偶联，得到了[三（烷氧基二甲基硅基）甲基]烷基二茂铁，收率良好至极佳。在 1,8- 二氮杂双环[5.4.0]十一碳-7-烯催化剂存在下，4-[三（苄氧基二甲基硅基）甲基]丁基二茂铁与苄醇发生乙醚化反应，也制备出了 4-[三（甲氧基二甲基硅基）甲基]丁基二茂铁。
• Lewis Acid-Mediated β-Hydride Abstraction Reactions of Divalent M(C(SiHMe₂)₃)₂THF₂ (M = Ca, Yb)
  作者：KaKing Yan、Brianna M. Upton、Arkady Ellern、Aaron D. Sadow

  DOI：10.1021/ja9070865

  日期：2009.10.28

  calcium and ytterbium compounds M(C(SiHMe(2))(3))(2)THF(2) contain beta-agostic SiH groups, as determined by spectroscopy and crystallography. Upon thermolysis, HC(SiHMe(2))(3) is formed. However, the SiH groups are hydridic. The compounds M(C(SiHMe(2))(3))(2)THF(2) react with 1 and 2 equiv of the Lewis acid B(C(6)F(5))(3) to form MC(SiHMe(2))(3)HB(C(6)F(5))(3))THF(2) and M(HB(C(6)F(5))(3))(2)THF(2), respectively

  二价钙和镱化合物 M(C(SiHMe(2))(3))(2)THF(2) 包含β-agostic SiH 组，由光谱学和晶体学确定。热解时，会形成 HC(SiHMe(2))(3)。然而，SiH 基团是氢化的。化合物 M(C(SiHMe(2))(3))(2)THF(2) 与 1 和 2 当量的路易斯酸 B(C(6)F(5))(3) 反应形成 MC( SiHMe(2))(3)HB(C(6)F(5))(3))THF(2) 和 M(HB(C(6)F(5))(3))(2)THF( 2) 分别。这些物质包含来自氢化物提取的阴离子 [HB(C(6)F(5))(3)](-) 而不是 [(Me(2)HSi)(3)CB(C(6)F(5) )(3)](-) 来自烷基提取。1,3-二硅杂环丁烷副产品最初建议β-消除[作为silene Me(2)Si 水平线C(SiHMe(2))(2) 的二聚体]，但其他产品和反应化