(phenyl)silyldiazomethane | 288305-41-9

• 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: (phenyl)silyldiazomethane
• 英文别名: Diazomethyl(phenyl)silane；diazomethyl(phenyl)silane
• CAS: 288305-41-9
• 化学式: C₇H₈N₂Si
• 分子量: 148.239
• InChiKey: LIZXTBBFDNOOLQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.26
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (phenyl)silyldiazomethane 生成 methyl(phenyl)silylene
  参考文献：
  名称：

  Oxidation of Methyl(phenyl)silyleneSynthesis of a Dioxasilirane

  摘要：

  The oxidation of methyl(phenyl)silylene, 3f, with molecular oxygen is investigated using matrix isolation spectroscopy in combination with DFT calculations. The UV irradiation (lambda > 305 nm) of phenylsilyldiazomethane, 8, matrix-isolated in argon at 10 K, produces silylene 3f in very high yield. In O-2 doped argon matrixes, the thermal reaction of 3f with O-2 could be directly monitored by IR spectroscopy. The only reaction product is dioxasilirane 5f, presumably formed via cyclization of silanone O-oxide 4f. DFT calculations reveal that the activation barrier for the 4f --> 5f cyclization is less than 1 kcal/mol, too small to allow the matrix isolation of 4f. Dioxasilirane 5f is photolabile, and irradiation with blue light (lambda > 420 nm) results in a [1,2]-phenyl migration to give silaester 7f. The product of the methyl migration, silaester 13, is formed as a minor constituent.

  DOI：

  10.1021/ja000192y
• 作为产物：
  描述：

  二苯基硅烷 在 N,N-二异丙基乙胺 作用下， 以 乙醚 为溶剂， 生成 (phenyl)silyldiazomethane
  参考文献：
  名称：

  Reactions of methyl(phenyl)silylene with CO and PH3—the formation of acid–base complexes

  摘要：

  The thermal reaction of methyl(phenyl)silylene 1a with CO and PH3, respectively, was investigated using matrix isolation spectroscopy in combination with DFT calculations. The silylene la was produced by UV irradiation (gimel > 400 nm followed by gimel > 350 nm) of (phenyl)silyldiazomethane 2 in high yields. The thermal reaction of 2 with CO in CO-doped argon matrices produces the acid-base adduct 3 which was identified by IR and UV spectroscopy. The analogous reaction with PH3 produced the acid-base adduct 4. Complex 4 is photolabile and on irradiation with UV light (gimel > 350 nm) rearranges to methylphenyl(phosphino)silane 5, the product of the insertion of the silicon atom into a PH bond. (C) 2002 Published by Elsevier Science B.V.

  DOI：

  10.1016/s0022-328x(01)01363-8

文献信息

• Oxidation of Methyl(phenyl)silyleneSynthesis of a Dioxasilirane
  作者：Holger Bornemann、Wolfram Sander

  DOI：10.1021/ja000192y

  日期：2000.7.1

  The oxidation of methyl(phenyl)silylene, 3f, with molecular oxygen is investigated using matrix isolation spectroscopy in combination with DFT calculations. The UV irradiation (lambda > 305 nm) of phenylsilyldiazomethane, 8, matrix-isolated in argon at 10 K, produces silylene 3f in very high yield. In O-2 doped argon matrixes, the thermal reaction of 3f with O-2 could be directly monitored by IR spectroscopy. The only reaction product is dioxasilirane 5f, presumably formed via cyclization of silanone O-oxide 4f. DFT calculations reveal that the activation barrier for the 4f --> 5f cyclization is less than 1 kcal/mol, too small to allow the matrix isolation of 4f. Dioxasilirane 5f is photolabile, and irradiation with blue light (lambda > 420 nm) results in a [1,2]-phenyl migration to give silaester 7f. The product of the methyl migration, silaester 13, is formed as a minor constituent.
• Reactions of methyl(phenyl)silylene with CO and PH3—the formation of acid–base complexes
  作者：Holger Bornemann、Wolfram Sander

  DOI：10.1016/s0022-328x(01)01363-8

  日期：2002.1

  The thermal reaction of methyl(phenyl)silylene 1a with CO and PH3, respectively, was investigated using matrix isolation spectroscopy in combination with DFT calculations. The silylene la was produced by UV irradiation (gimel > 400 nm followed by gimel > 350 nm) of (phenyl)silyldiazomethane 2 in high yields. The thermal reaction of 2 with CO in CO-doped argon matrices produces the acid-base adduct 3 which was identified by IR and UV spectroscopy. The analogous reaction with PH3 produced the acid-base adduct 4. Complex 4 is photolabile and on irradiation with UV light (gimel > 350 nm) rearranges to methylphenyl(phosphino)silane 5, the product of the insertion of the silicon atom into a PH bond. (C) 2002 Published by Elsevier Science B.V.