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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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| Authors: | Dr. Zhongshu Li Dr. Xiaodan Chen Dr. Zoltán Benkő Liu Liu Dr. David A. Ruiz Jesse L. Peltier Prof. Dr. Guy Bertrand Prof. Dr. Chen‐Yong Su Prof. Dr. Hansjörg Grützmacher |
| Affiliation: | 1. Lehn Institute of Functional Materials (LIFM), Sun Yat-Sen University, Guangzhou, China;2. Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland;3. Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Budapest, Hungary;4. UCSD/CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California San Diego, La Jolla, CA, USA |
| Abstract: | 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. |
| Keywords: | constitution cyanates fulminates isomerism phosphorus |