Cyclo-oligomerization of isocyanates with Na(PH2) or Na(OCP) as “P−” anion sources

Heift, D.; Benkő, Z.; Grützmacher, H.; Jupp, A.R.; Goicoechea, J.M.

doi:10.1039/c5sc00963d

Cyclo-oligomerization of isocyanates with Na(PH2) or Na(OCP) as “P−” anion sources

Heift, D.; Benkő, Z.; Grützmacher, H.; Jupp, A.R.; Goicoechea, J.M.

Authors

Dr Dominikus Heift dominikus.heift@durham.ac.uk
Academic Visitor

Z. Benkő

H. Grützmacher

A.R. Jupp

J.M. Goicoechea

Abstract

We show that the 2-phosphaethynolate anion, OCP−, is a simple and efficient catalyst for the cyclotrimerization of isocyanates. This process proceeds step-wise and involves five-membered heterocycles, namely 1,4,2-diazaphospholidine-3,5-dionide anions and spiro-phosphoranides as detectable intermediates, both of which were also found to be involved in the catalytic conversion. These species can be considered as adducts of a phosphide anion with two and four isocyanate molecules, respectively, demonstrating that the OCP− anion acts as a formal “P−” source. The interconversion between these anionic species was found to be reversible, allowing them to serve as reservoirs for unique phosphorus-based living-catalysts for isocyanate trimerization.

Citation

Heift, D., Benkő, Z., Grützmacher, H., Jupp, A., & Goicoechea, J. (2015). Cyclo-oligomerization of isocyanates with Na(PH2) or Na(OCP) as “P−” anion sources. Chemical Science, 6(7), 4017-4024. https://doi.org/10.1039/c5sc00963d

Journal Article Type	Article
Acceptance Date	Apr 29, 2015
Online Publication Date	May 13, 2015
Publication Date	Jul 1, 2015
Deposit Date	Feb 22, 2017
Publicly Available Date	Mar 28, 2017
Journal	Chemical Science
Print ISSN	2041-6520
Electronic ISSN	2041-6539
Publisher	Royal Society of Chemistry
Peer Reviewed	Peer Reviewed
Volume	6
Issue	7
Pages	4017-4024
DOI	https://doi.org/10.1039/c5sc00963d