Issue 7, 2015

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

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
17 Mar 2015
Accepted
29 Apr 2015
First published
13 May 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 4017-4024

Author version available

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

D. Heift, Z. Benkő, H. Grützmacher, A. R. Jupp and J. M. Goicoechea, Chem. Sci., 2015, 6, 4017 DOI: 10.1039/C5SC00963D

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