Heift, Dominikus, Benkő, Zoltán, Grützmacher, Hansjörg, Jupp, Andrew R. and Goicoechea, Jose M. (2015) Cyclo-oligomerization of isocyanates with Na(PH[sub]2) or Na(OCP) as "P-" anion sources. Chemical Science, 6(7), pp. 4017-4024. ISSN (print) 2041-6520
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.
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