title: N-Heterocyclic Carbenes as Promotors for the Rearrangement of Phosphaketenes to Phosphaheteroallenes: A Case Study for OCP to OPC Constitutional Isomerism.
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.
authors.affiliation: Lehn Institute of Functional Materials (LIFM), Sun Yat-Sen University, 1510275, Guangzhou, China.
authors.forename: Zhongshu
authors.initials: Z
authors.lastname: Li
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zurich, 8093, Zurich, Switzerland.
authors.forename: Xiaodan
authors.initials: X
authors.lastname: Chen
authors.affiliation: Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, 1111, Budapest, Hungary.
authors.forename: Zoltán
authors.initials: Z
authors.lastname: Benkő
authors.affiliation: UCSD/CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California San Diego, La Jolla, CA, 92521-0403, USA.
authors.forename: Liu Leo
authors.initials: LL
authors.lastname: Liu
authors.affiliation: UCSD/CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California San Diego, La Jolla, CA, 92521-0403, USA.
authors.forename: David A
authors.initials: DA
authors.lastname: Ruiz
authors.affiliation: UCSD/CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California San Diego, La Jolla, CA, 92521-0403, USA.
authors.forename: Jesse L
authors.initials: JL
authors.lastname: Peltier
authors.affiliation: UCSD/CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California San Diego, La Jolla, CA, 92521-0403, USA. guybertrand@ucsd.edu.
authors.forename: Guy
authors.initials: G
authors.lastname: Bertrand
authors.affiliation: Lehn Institute of Functional Materials (LIFM), Sun Yat-Sen University, 1510275, Guangzhou, China. cesscy@mail.sysu.edu.cn.
authors.forename: Chen-Yong
authors.initials: CY
authors.lastname: Su
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zurich, 8093, Zurich, Switzerland. hgruetzmacher@ethz.ch.
authors.forename: Hansjörg
authors.identifier: 0000-0002-1531-8906
authors.initials: H
authors.lastname: Grützmacher
keywords: constitution; cyanates; fulminates; isomerism; phosphorus