O-ylide and π-complex formation in reactions of a carbene with dibenzo and monobenzo crown ethers.
O-ylide and π-complex formation in reactions of a carbene with dibenzo and monobenzo crown ethers.
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卡宾与二苯并和单苯并冠醚反应中形成 O-叶立德和 π-络合物。
DOI：
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发表时间：
2014
影响因子：
2.9
通讯作者：
K. Krogh
中科院分区：
文献类型：
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作者：
Pablo A. Hoijemberg;R. Moss;D. Feinblum;K. Krogh
对硝基苯基氯卡宾 (PNPCC) 与各种二苯并冠醚反应生成 O-叶立德和 π-配合物；可以通过卡宾和产物的光谱特征来跟踪反应。 O-叶立德形成速度最快，但随着时间的推移，它们会衰变，转而形成更稳定的π-配合物。广泛的计算研究支持并完善了适当的结构和机械猜想。 PNPCC 与单苯并冠醚的反应仅提供 O-叶立德的光谱特征；单苯并π-配合物要么不会以显着浓度形成，要么在光谱上是沉默的。
Reactions of p-nitrophenylchlorocarbene (PNPCC) with various dibenzo crown ethers produce O-ylides and π-complexes; the reactions can be followed via the spectral signatures of the carbene and the products. The O-ylides form most rapidly, but over time they decay in favor of the more stable π-complexes. Extensive computational studies support and refine appropriate structural and mechanistic conjectures. Reactions of PNPCC with monobenzo crown ethers afford only the spectral signatures of O-ylides; monobenzo π-complexes are either not formed in significant concentrations or are spectroscopically silent.