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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
Author(s) -
Li Zhongshu,
Chen Xiaodan,
Benkő Zoltán,
Liu Liu Leo,
Ruiz David A.,
Peltier Jesse L.,
Bertrand Guy,
Su ChenYong,
Grützmacher Hansjörg
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201600903
Subject(s) - isomerization , chemistry , molecule , structural isomer , stereochemistry , reaction mechanism , medicinal chemistry , catalysis , computational chemistry , organic chemistry
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.