N-Heterocyclic Carbenes as Promotors for the Rearrangement of Phosphaketenes to Phosphaheteroallenes: A Case Study for OCP to OPC Constitutional Isomerism

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• 作者：Dr. Zhongshu Li ; Dr. Xiaodan Chen ; Dr. Zolt&#225 ; n Benkő ; Liu Liu ; Dr. David A. Ruiz ; Jesse L. Peltier ; Prof. Dr. Guy Bertrand ; Prof. Dr. Chen-Yong Su and Prof. Dr. Hansjö ; rg Grü ; tzmacher
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：May 10, 2016
• 年：2016
• 卷：128
• 期：20
• 页码：6122-6126
• 全文大小：1067K
• ISSN：1521-3757

文摘

The concept of isomerism is essential to chemistry and allows defining molecules with an identical composition but different connectivity (bonds) between their atoms (constitutional isomers) and/or a different arrangement in space (stereoisomers). The reaction of phosphanyl ketenes, (NHP)−P=C=O (NHP=N-heterocyclic phosphenium) with N-heterocyclic carbenes (NHCs) leads to phosphaheteroallenes (NHP)−O−P=C=NHC in which the PCO unit has been isomerized to OPC. Based on the isolation of several intermediates and DFT calculations, a mechanism for this fundamental isomerisation process is proposed.