Details

Autor(en) / Beteiligte

• Heift, Dominikus
• Benkő, Zoltán
• Grützmacher, Hansjörg
• Jupp, Andrew R
• Goicoechea, Jose M

Titel

Cyclo-oligomerization of isocyanates with Na(PH 2 ) or Na(OCP) as "P - " anion sources

Ist Teil von

• Chemical science (Cambridge), 2015-07, Vol.6 (7), p.4017-4024

Ort / Verlag

England

Erscheinungsjahr

2015

Link zum Volltext

Quelle

Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals

Beschreibungen/Notizen

• 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.