diphenylcarbene-d₁₀ | 61695-67-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diphenylcarbene-d₁₀
• 英文别名: perdeuterated diphenylcarbene；d10-diphenylcarbene；Perdeuterodiphenylmethylen-Radikal；bis-pentadeuteriophenyl-methanediyl；decadeuterio-benzhydrylidene
• CAS: 61695-67-8
• 化学式: C₁₃H₁₀
• 分子量: 176.143
• InChiKey: XMGMFRIEKMMMSU-LHNTUAQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.16
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  diphenylcarbene-d₁₀ 生成
  参考文献：
  名称：

  1-苯基-1,2,4,6-环庚酸酯：缺少的二苯基碳烯中间体到芴重排

  摘要：

  通过UV-Vis，IR和EPR光谱研究了在3-5 K下在氩气中分离的基质中二苯卡宾5的光化学性质。尽管卡宾5证明对宽带UV辐射稳定，但在445 nm二极管激光器的强光照射期间，它会缓慢重排为1-苯基-1,2,4,6-环庚酸酯8。未观察到其他中间体。在将5重排为芴7的拟议机制中，丙二烯8是关键中间体。版权所有©2014 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/poc.3355
• 作为产物：
  描述：

  <²H10>diphenyldiazomethane 生成 diphenylcarbene-d₁₀
  参考文献：
  名称：

  1-苯基-1,2,4,6-环庚酸酯：缺少的二苯基碳烯中间体到芴重排

  摘要：

  通过UV-Vis，IR和EPR光谱研究了在3-5 K下在氩气中分离的基质中二苯卡宾5的光化学性质。尽管卡宾5证明对宽带UV辐射稳定，但在445 nm二极管激光器的强光照射期间，它会缓慢重排为1-苯基-1,2,4,6-环庚酸酯8。未观察到其他中间体。在将5重排为芴7的拟议机制中，丙二烯8是关键中间体。版权所有©2014 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/poc.3355

文献信息

• Study of the electronic structure and spectra of diphenylcarbene conformers in their ground state and lower excited states
  作者：A. Despres、V. Lejeune、E. Migirdicyan、A. Admasu、M. S. Platz、G. Berthier、O. Parisel、J. P. Flament、I. Baraldi、F. Momicchioli

  DOI：10.1021/j100152a048

  日期：1993.12

  The triplet-triplet fluorescence of perprotonated and perdeuterated diphenylcarbene (DPC-h10 and -d10) in n-hexane at 4.2-25 K are both composed of a sharp spectrum and a broad blue-shifted one. They are attributed to two different conformers, the sharp spectrum corresponding to DPC in a quasi-planar geometry. The excitation spectra of both emissions consist of broadbands with a large Stokes shift. A detailed CS-INDO CI investigation (configuration interaction based on an intermediate neglect differential overlap method adapted to conformation and spectroscopy problems) is performed for three different geometries of DPC having C2v, C2, and C1 symmetries. The computed triplet-triplet transition energies which indicate an hypsochromic shift going from planar C2v to nonplanar C1 structures compare favorably with the experimental data. The fluorescence decays of DPC-h10 and -d10 are nonexponential and attributed to the emission from different sublevels of the first excited triplet state. The measured decays of the broad fluorescence are longer than those of the sharp one. This is in agreement with CS-INDO CI calculations which predict a decrease of the oscillator strength of the T0-T1 transition going from C2v to C1 structures, as due to the inversion between the two excited triplets corresponding to the n-pi*1 and npi*2 configurations. The zero-field splitting (ZFS) parameter D(T1) of DPC in the first excited triplet T1 has been estimated from the magnetic field effect on the fluorescence decays. D(T1) = 0.007 and 0.20 cm-1 for measurements carried out respectively on the sharp and on the broad fluorescence. Tentative ZFS calculations give D(T1) = 0.01 55 cm-1 for the C2v structure and D(T1) = 0.01 15 cm-1 for the C1 structure. The measured and calculated D(T1) values are always smaller than the D(T0) = 0.405 cm-1 value of DPC in the ground triplet state, which indicates the delocalization of the pi electron density onto the aromatic rings upon excitation. It is therefore reasonable to detect a specific chemistry of this carbene in the presence of an intense laser which creates a high concentration of DPC in the first excited triplet T1.