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.

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
• Public URL: https://durham-repository.worktribe.com/output/1362771