Publication details for Dr Dominikus HeiftHeift, D., Benkő, Z., Grützmacher, H., Jupp, A. R. & Goicoechea, J. M. (2015). Cyclo-oligomerization of isocyanates with Na(PH2) or Na(OCP) as “P−” anion sources. Chemical Science 6(7): 4017-4024.
- Publication type: Journal Article
- ISSN/ISBN: 2041-6520 (print), 2041-6539 (electronic)
- DOI: 10.1039/C5SC00963D
- Further publication details on publisher web site
- Durham Research Online (DRO) - may include full text
Author(s) from Durham
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.