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

Zhongshu Li; Xiaodan Chen; Zoltán Benkő; Liu Leo Liu; David A Ruiz; Jesse L Peltier; Guy Bertrand; Chen-Yong Su; Hansjörg Grützmacher

doi:10.1002/anie.201600903

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

Angew Chem Int Ed Engl. 2016 May 10;55(20):6018-22. doi: 10.1002/anie.201600903. Epub 2016 Apr 8.

Authors

Zhongshu Li¹, Xiaodan Chen², Zoltán Benkő³, Liu Leo Liu⁴, David A Ruiz⁴, Jesse L Peltier⁴, Guy Bertrand⁵, Chen-Yong Su⁶, Hansjörg Grützmacher⁷

Affiliations

¹ Lehn Institute of Functional Materials (LIFM), Sun Yat-Sen University, 1510275, Guangzhou, China.
² Department of Chemistry and Applied Biosciences, ETH Zurich, 8093, Zurich, Switzerland.
³ Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, 1111, Budapest, Hungary.
⁴ UCSD/CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California San Diego, La Jolla, CA, 92521-0403, USA.
⁵ UCSD/CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California San Diego, La Jolla, CA, 92521-0403, USA. guybertrand@ucsd.edu.
⁶ Lehn Institute of Functional Materials (LIFM), Sun Yat-Sen University, 1510275, Guangzhou, China. cesscy@mail.sysu.edu.cn.
⁷ Department of Chemistry and Applied Biosciences, ETH Zurich, 8093, Zurich, Switzerland. hgruetzmacher@ethz.ch.

PMID: 27060924
DOI: 10.1002/anie.201600903

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.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't