trimethylsilanylium | 28927-31-3

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: trimethylsilanylium
• CAS: 28927-31-3
• 化学式: C₃H₉Si
• 分子量: 73.19
• InChiKey: VOYMPSZBODLRKS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.37
• 重原子数：
  4
• 可旋转键数：
  0
• 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：

  trimethylsilanylium 在 水 作用下， 生成 Trimethylsilyloxidanium
  参考文献：
  名称：

  Stone, John A.; Wojtyniak, Anastasia C. M.; Wytenburg, Willum, Canadian Journal of Chemistry, 1986, vol. 64, p. 575 - 576

  摘要：

  DOI：
• 作为产物：
  描述：

  四甲基硅烷 在 氧气 、 三乙胺 作用下， 以 gas 为溶剂， 120.0 ℃ 、93.33 kPa 条件下， 生成 trimethylsilanylium
  参考文献：
  名称：

  Internal Solvation Effects on the Reactivity of .alpha.,.omega.-Diphenylalkanes toward Me3C+ Ions

  摘要：

  The reactivity of alpha,omega-diphenylalkanes (1 less than or equal to n less than or equal to 4) toward Me(3)C(+) ions has been investigated with the radiolytic technique at 720 Torr, at temperatures of 47 and 120 degrees C. The intramolecular isotopic discrimination of Me(3)C(+), favoring attack at the unlabeled ring of C6H5(CH2)(2)C6D5 by a factor of 1.5 at 120 degrees C, contrasts with the lack of intermolecular isotopic discrimination, reflected by the same reactivity toward (C6H5CH2)(2) and (C6D5CH2)(2). Competition experiments show an appreciably higher reactivity of Ph(CH2)(n)Ph (n = 2-4) relative to toluene and diphenylmethane (DPM), but, when Ph(CH2)(n)Ph (n = 3, 4) or (3-CH3C6H4)(CH2)(2)C6H5 compete with Ph(CH2)(2)Ph, relative reactivities level off. The lack of substrate selectivity, in contrast to an intramolecular discrimination in the tert-butylation of (3-CH3C6H4)(CH2)(2)C6H5 of a factor of 2, together with the related variation of kinetic isotope effects, points out the kinetic role of the collision complex 1 from Me(3)C(+) and diphenylalkanes. The additional (''spectator'') ring of the higher homologues Ph(CH2)(n)Ph (n = 2-4) prevents dissociation of 1, making its formation irreversible and causing tert-butylation to occur at the encounter rate, in contrast to DPM, whose second ring appears essentially inert. Experiments involving substitution by Me(3)Si(+) at 120 degrees C show that this electrophile attacks preferably the unlabeled ring of C6H5(CH2)(2)C6D5 by a factor of 1.5, consistent with the 1.4 times higher reactivity toward (C6H5CH2)(2) With respect to (C6D5CH2)(2). In this case, the isotopic discrimination is traced to the competition between desilylation and deprotonation of intermediate ipso-silylated arenium ions.

  DOI：

  10.1021/j100010a026

文献信息

• Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
  作者：Rocío Velasco、Carlos Silva López、Olalla Nieto Faza、Roberto Sanz

  DOI：10.1002/chem.201602254

  日期：2016.10.10

  different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron‐poor aryl groups that favor the anionic pathway.

  通过仔细控制反应温度，用t BuLi处理芳基苄基醚有选择地导致α-锂化，生成稳定的有机锂，这些有机锂可以在被预期的[1,2] -Wittig吸附之前直接被多种选择的亲电试剂捕获。重排。这种重排已在实验和计算上进行了深入研究，使用了在芳基环上带有不同取代基的芳基α锂化苄基醚。获得的结果支持了协同的阴离子分子内添加/消除序列和自由基解离/重组序列的能力，用于解释芳基迁移的趋势。对于具有有利于阴离子途径的电子贫芳基的底物，发现了更有利的重排。
• Kinetics of hydride-transfer reactions from hydrosilanes to carbenium ions. Substituent effects in silicenium ions
  作者：Herbert Mayr、Nils Basso、Gisela Hagen

  DOI：10.1021/ja00034a044

  日期：1992.4

  varying substitution to para-substituted diarylcarbenium ions have been measured in dichloromethane solution. Generally the reactions follow a second-order rate law, -d[Ar 2 CH + ]/dt=k 2 [Ar 2 CH + ] [HSiR 1 R 2 R 3 ], and k 2 is independent of the degree of ion-pairing and the nature of the counterion (exceptions are reported). The reaction rates are almost independent of solvent polarity

  已经在二氯甲烷溶液中测量了氢化物从具有广泛变化的取代基的氢硅烷 HSiR 1 R 2 R 3 到对位取代的二芳基碳鎓离子的转移速率。通常反应遵循二阶速率定律，-d[Ar 2 CH + ]/dt=k 2 [Ar 2 CH + ] [HSiR 1 R 2 R 3 ]，k 2 与离子的程度无关-配对和反离子的性质（报告了例外情况）。反应速率几乎与溶剂极性无关
• Ion chemistry in tetramethylsilane (CH3)4Si
  作者：S. McGinnis、K. Riehl、P.D. Haaland

  DOI：10.1016/0009-2614(94)01313-k

  日期：1995.1

  The cross sections for simple and dissociative ionization of tetramethylsilane ((CH3)4Si or TMS) by electron impact have been measured using Fourier-transform mass spectrometry. The total ionization cross section is 8.5 x 10−16 cm2 between 30 and 70 eV. The molecular ion is Jahn-Teller unstable, with dissociative ionization to form (CH3)3Si+ dominating the mass spectrum. CH3SiH2+ and CH3Si+ react rapidly

  已经通过傅里叶变换质谱法测量了四甲基硅烷（（CH 3）4 Si或TMS）通过电子撞击进行简单和解离电离的横截面。总电离横截面在30至70 eV之间为8.5 x 10 -16 cm 2。该分子离子是Jahn-Teller不稳定的，具有离解电离形成（CH 3）3 Si +占主导地位的质谱。CH 3 SiH 2 +和CH 3 Si +与TMS快速反应生成（CH 3）3 Si +。（CH3）3 Si +不与TMS反应，但会被背景水蒸气缓慢水合。
• Chemical Ionization of TNT and RDX with Trimethylsilyl Cation
  作者：Kevin C. Crellin、M. Widmer、J. L. Beauchamp

  DOI：10.1021/ac961003q

  日期：1997.3.1

  Fourier transform ion cyclotron resonance mass spectrometry has been used to examine the reactions of Si(CH3)3+ with nitrobenzene, TNT, and RDX. With nitrobenzene, the only reaction observed is adduct formation which generates the C6H5NO2Si(CH3)3+ ion. The bimolecular rate constant for the reaction of Si(CH3)3+ with nitrobenzene is measured to be 1.8 × 10-9 cm3 s-1 molecule-1. With TNT, fragmentation and adduct formation were observed. The bimolecular rate constant for the reaction of Si(CH3)3+ with TNT is measured to be 0.85 × 10-9 cm3 s-1 molecule-1. With RDX, the dominant reaction observed is adduct formation, but some fragmentation is seen as a minor reaction pathway. The bimolecular rate constant for the reaction of Si(CH3)3+ with RDX is estimated to be similar to that observed with TNT (∼0.7 × 10-9 cm3 s-1 molecule-1). Collision-induced dissociation experiments performed on both the TNT−Si(CH3)3+ and the RDX−Si(CH3)3+ adducts using off-resonance collisional activation show the same fragmentation pattern that is observed during adduct formation. This fragmentation pattern appears to be a “fingerprint” for both adducts. These reactions appear to be driven by the high affinity of Si for oxygen and the attraction of the Si(CH3)3+ ion to the formal negative charge of oxygen in a nitro group. A reaction coordinate diagram for reactions of RDX with Si(CH3)3+ is derived (from known thermochemistry and ab initio calculations on the reactive intermediates) and its implications are discussed. Reactions of this type could be useful as a detection scheme for common explosives.

  傅里叶变换离子回旋共振质谱已被用于研究Si(CH3)3+与硝基苯、TNT（三硝基甲苯）和RDX（环三亚甲基三硝胺）的反应。与硝基苯的反应观察到的唯一现象是加合物的形成，生成了C6H5NO2Si(CH3)3+离子。Si(CH3)3+与硝基苯反应的双分子速率常数测得为1.8 × 10-9 cm3 s-1 molecule-1。与TNT反应时，观察到了碎裂和加合物的形成。Si(CH3)3+与TNT反应的双分子速率常数测得为0.85 × 10-9 cm3 s-1 molecule-1。与RDX反应时，主要观察到的是加合物的形成，但也有一些碎裂作为次要反应途径。Si(CH3)3+与RDX反应的双分子速率常数估计与TNT的观察值相似（约0.7 × 10-9 cm3 s-1 molecule-1）。在TNT−Si(CH3)3+和RDX−Si(CH3)3+加合物上进行的碰撞诱导解离实验（使用非共振碰撞活化）显示，在加合物形成过程中观察到的碎裂模式相同。这种碎裂模式似乎是这两种加合物的“指纹”。这些反应似乎是由硅对氧的高亲和力以及Si(CH3)3+离子对硝基中形式负电荷氧的吸引所驱动的。从已知的 热化学和反应中间体的从头计算中得出了RDX与Si(CH3)3+反应的反应坐标图，并讨论了其含义。这类反应可能有助于作为常见炸药的检测方案。
• The 2-(trimethylsilyl)ethoxymethoxy (OSEM) directed ortho metalation group. New regiospecific synthetic routes to substituted benzenes and pyridines
  作者：Saumitra Sengupta、Victor Snieckus

  DOI：10.1016/s0040-4039(00)97597-x

  日期：——

  Regiospecific metalation of OSEM aryl (2) and 3-pyridyl (5) systems allows the preparation of diversely substituted aromatic (3, Table), 4-pyridyl (6), and, significantly, 2-pyridyl (7,9) derivatives.

  OSEM芳基（2）和3-吡啶基（5）系统的区域特异性金属化可以制备不同取代的芳族化合物（3，表），4-吡啶基（6）以及明显的2-吡啶基（7,9）衍生物。