Nitroso-trimethyl-silan | 154317-75-6

• 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: Nitroso-trimethyl-silan
• 英文别名: Trimethyl(nitroso)silane
• CAS: 154317-75-6
• 化学式: C₃H₉NOSi
• 分子量: 103.196
• InChiKey: UAVHHTWLPRHEKX-UHFFFAOYSA-N

物化性质

• 沸点：
  57.2±23.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.59
• 重原子数：
  6
• 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：
  29.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Nitroso-trimethyl-silan 在 nitric oxide 作用下， 以 gaseous matrix 为溶剂， 生成 三甲基硅烷基自由基
  参考文献：
  名称：

  Si（CH3）3 + NO反应的动力学和热化学：直接确定Si-N键能

  摘要：

  The reaction of trimethylsilyl radicals with nitric oxide, Si(CH3)(3) + NO reversible arrow Si(CH3)(3)NO, has been studied using pulsed excimer-laser photolysis coupled with time-resolved photoionization mass spectrometry over the temperature range 300-812 K. The reaction rate constant was measured as a function of temperature and density (He) in the range 0.82 x 10(16) [He] 15.7 x 10(16) molecules cm(-3). Equilibrium constants for the reaction were measured between 685 and 787 K. The standard enthalpy of the reaction Si(CH3)(3) + NO reversible arrow Si(CH3)(3)NO was obtained from the measured equilibrium constants using both second- and third-law methods. The two procedures yielded results in good agreement: Delta H-298(o) = -183 + 11 kJ mol(-1) (second law) and Delta H-298(o) = -190.2 +/- 3.6 kJ mol(-1) (third law), the latter being more accurate. The high-pressure-limit rate constant of reaction Si(CH3)(3) +/- NO --> Si(CH3)(3)NO, obtained by a short extrapolation of the experimental data using the Troe factorization technique, has a small negative temperature dependence: k(infinity.rec) = (3.8 +/- 0.4) x 10-(11) (T/298)(-(0.6) (+/-) (0.2)). Ab initio calculations with empirical bond additivity corrections have been performed to determine the structure, vibrational frequencies, and energies of the low-lying electronic singlet and triplet states of the Si(CH3)(3)NO molecule. The calculated thermodynamic functions of the molecule were used to obtain the standard entropy of the reaction (Delta S-298(o) = -147.9 J mol(-1) K-1) that was used in the third-law thermochemical calculations. The theoretical standard enthalpy of the reaction, Delta H-298(o)(calc) = -190.9 kT mol(-1), is in excellent agreement with that determined experimentally using the third-law procedure. The intrinsic Si(CH3)(3)-NO bond strength of 187.4 +/- 4.0 kJ mol(-1) (-Delta H-0(o) for the reaction) was determined using the measured enthalpy of the reaction at 298 K (by the third-law method) and the calculated relative enthalpy functions. This study provides the first direct experimental determination of a Si-N bond strength.

  DOI：

  10.1021/j100039a023
• 作为产物：
  描述：

  三甲基硅烷基自由基 在 nitric oxide 作用下， 以 gaseous matrix 为溶剂， 生成 Nitroso-trimethyl-silan
  参考文献：
  名称：

  Si（CH3）3 + NO反应的动力学和热化学：直接确定Si-N键能

  摘要：

  The reaction of trimethylsilyl radicals with nitric oxide, Si(CH3)(3) + NO reversible arrow Si(CH3)(3)NO, has been studied using pulsed excimer-laser photolysis coupled with time-resolved photoionization mass spectrometry over the temperature range 300-812 K. The reaction rate constant was measured as a function of temperature and density (He) in the range 0.82 x 10(16) [He] 15.7 x 10(16) molecules cm(-3). Equilibrium constants for the reaction were measured between 685 and 787 K. The standard enthalpy of the reaction Si(CH3)(3) + NO reversible arrow Si(CH3)(3)NO was obtained from the measured equilibrium constants using both second- and third-law methods. The two procedures yielded results in good agreement: Delta H-298(o) = -183 + 11 kJ mol(-1) (second law) and Delta H-298(o) = -190.2 +/- 3.6 kJ mol(-1) (third law), the latter being more accurate. The high-pressure-limit rate constant of reaction Si(CH3)(3) +/- NO --> Si(CH3)(3)NO, obtained by a short extrapolation of the experimental data using the Troe factorization technique, has a small negative temperature dependence: k(infinity.rec) = (3.8 +/- 0.4) x 10-(11) (T/298)(-(0.6) (+/-) (0.2)). Ab initio calculations with empirical bond additivity corrections have been performed to determine the structure, vibrational frequencies, and energies of the low-lying electronic singlet and triplet states of the Si(CH3)(3)NO molecule. The calculated thermodynamic functions of the molecule were used to obtain the standard entropy of the reaction (Delta S-298(o) = -147.9 J mol(-1) K-1) that was used in the third-law thermochemical calculations. The theoretical standard enthalpy of the reaction, Delta H-298(o)(calc) = -190.9 kT mol(-1), is in excellent agreement with that determined experimentally using the third-law procedure. The intrinsic Si(CH3)(3)-NO bond strength of 187.4 +/- 4.0 kJ mol(-1) (-Delta H-0(o) for the reaction) was determined using the measured enthalpy of the reaction at 298 K (by the third-law method) and the calculated relative enthalpy functions. This study provides the first direct experimental determination of a Si-N bond strength.

  DOI：

  10.1021/j100039a023

文献信息

• Kinetics and thermochemistry of Si(CH3)3 + NO reaction: direct determination of a Si-N bond energy
  作者：Lev N. Krasnoperov、Jukka T. Niiranen、David Gutman、Carl F. Melius、Mark D. Allendorf

  DOI：10.1021/j100039a023

  日期：1995.9

  The reaction of trimethylsilyl radicals with nitric oxide, Si(CH3)(3) + NO reversible arrow Si(CH3)(3)NO, has been studied using pulsed excimer-laser photolysis coupled with time-resolved photoionization mass spectrometry over the temperature range 300-812 K. The reaction rate constant was measured as a function of temperature and density (He) in the range 0.82 x 10(16) [He] 15.7 x 10(16) molecules cm(-3). Equilibrium constants for the reaction were measured between 685 and 787 K. The standard enthalpy of the reaction Si(CH3)(3) + NO reversible arrow Si(CH3)(3)NO was obtained from the measured equilibrium constants using both second- and third-law methods. The two procedures yielded results in good agreement: Delta H-298(o) = -183 + 11 kJ mol(-1) (second law) and Delta H-298(o) = -190.2 +/- 3.6 kJ mol(-1) (third law), the latter being more accurate. The high-pressure-limit rate constant of reaction Si(CH3)(3) +/- NO --> Si(CH3)(3)NO, obtained by a short extrapolation of the experimental data using the Troe factorization technique, has a small negative temperature dependence: k(infinity.rec) = (3.8 +/- 0.4) x 10-(11) (T/298)(-(0.6) (+/-) (0.2)). Ab initio calculations with empirical bond additivity corrections have been performed to determine the structure, vibrational frequencies, and energies of the low-lying electronic singlet and triplet states of the Si(CH3)(3)NO molecule. The calculated thermodynamic functions of the molecule were used to obtain the standard entropy of the reaction (Delta S-298(o) = -147.9 J mol(-1) K-1) that was used in the third-law thermochemical calculations. The theoretical standard enthalpy of the reaction, Delta H-298(o)(calc) = -190.9 kT mol(-1), is in excellent agreement with that determined experimentally using the third-law procedure. The intrinsic Si(CH3)(3)-NO bond strength of 187.4 +/- 4.0 kJ mol(-1) (-Delta H-0(o) for the reaction) was determined using the measured enthalpy of the reaction at 298 K (by the third-law method) and the calculated relative enthalpy functions. This study provides the first direct experimental determination of a Si-N bond strength.