HMDSO-d9 | 127663-93-8

• 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: HMDSO-d9
• 英文别名: hexamethyldisiloxane-d₉；HMDSO-d₉
• CAS: 127663-93-8
• 化学式: C₆H₁₈OSi₂
• 分子量: 171.308
• InChiKey: UQEAIHBTYFGYIE-GQALSZNTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.67
• 重原子数：
  9.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  三甲基硅醇 、 三甲基氯硅烷-D9 在 三乙胺 作用下， 生成 HMDSO-d9
  参考文献：
  名称：

  Metastable ion study of organosilicon compounds part II—hexamethyldisiloxane

  摘要：

  AbstractUnimolecular reactions of the metastable silicenium ion (CH3)3SiOSi(CH3)2 + generated by dissociative ionization of bexamethyldisiloxane were investigated by mass‐analysed ion kinetic energy (PUKE) Spectrometry. The characteristic fragmentations observed were losses of CH4 and (CH3)2SiO molecules. Complete scrambling of all methyl groups prior to these reactions was found by investigating the MIKE spectra of deuterium labelled analogues (CD3)3SiOSi(CH3)2+ and (CH3)3SiOSi(CD3)3+. The loss of methane was accompanied by a large kinetic energy release (T0.5 = 482 meV). The MIKE spectra of silicenium ions were compared with those of their carbon analogues. The most predominant reaction of metastable (CH3)3COC(CH3)3+ ion was the loss of CH2C(C H3)2 leading to protonated acetone. Significant differences between the ion fragmention characteristics of silicon and carbon compounds were found.

  DOI：

  10.1002/oms.1210250109

文献信息

• Mechanism of Molybdenum-Mediated Carbon Monoxide Deoxygenation and Coupling: Mono- and Dicarbyne Complexes Precede C–O Bond Cleavage and C–C Bond Formation
  作者：Joshua A. Buss、Theodor Agapie

  DOI：10.1021/jacs.6b10535

  日期：2016.12.21

  electron-rich Mo center, favors deoxygenative pathways. From the bis(siloxycarbyne), isotopic labeling experiments and kinetics are consistent with a mechanism involving unimolecular silyl loss or C-O cleavage as rate-determining steps toward carbide formation. Reduction of Mo(IV) CO adducts of carbide and silylcarbyne species allowed for the spectroscopic detection of reduced silylcarbyne/CO and mixed silylc

  CO 与增值 C≥2 产品的脱氧偶联具有挑战性，并且在机理上知之甚少。在此，我们报告了对 CO 还原耦合的机理研究，为多电子键断裂和成键转换提供了新的基本见解。在我们的研究中，双（甲硅烷氧基羰基）配合物的形成先于 CO 键断裂。在 -78 °C 下，几天后，CC 耦合发生而没有 CO 裂解。然而，当升温至 0 °C 时，可以从这种双（甲硅烷氧基羰基）复合物中观察到 CO 裂解。甲硅烷氧基羰基/CO 物种在较低温度下发生 CO 键断裂，表明单甲硅烷基化和更富电子的 Mo 中心有利于脱氧途径。从双（甲硅烷氧基羰基），同位素标记实验和动力学与涉及单分子甲硅烷基损失或 CO 裂解作为碳化物形成的速率决定步骤的机制一致。碳化物和甲硅烷基碳炔物种的 Mo(IV) CO 加合物的还原允许分别对还原的甲硅烷基碳炔/CO 和混合的甲硅烷基碳炔/甲硅烷氧基碳炔配合物进行光谱检测。加热后，这两种甲硅烷基羰基都形成