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Cyclo-oligomerization of isocyanates with Na(PH2) or Na(OCP) as "P-" anion sources.
Journal article

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

  • Heift D Department of Chemistry and Applied Biosciences , ETH Zurich , CH-8093 Zurich , Switzerland . Email: hgruetzmacher@ethz.ch ; Email: benkoe@inorg.chem.ethz.ch.
  • Benkő Z Department of Chemistry and Applied Biosciences , ETH Zurich , CH-8093 Zurich , Switzerland . Email: hgruetzmacher@ethz.ch ; Email: benkoe@inorg.chem.ethz.ch.
  • Grützmacher H Department of Chemistry and Applied Biosciences , ETH Zurich , CH-8093 Zurich , Switzerland . Email: hgruetzmacher@ethz.ch ; Email: benkoe@inorg.chem.ethz.ch.
  • Jupp AR Department of Chemistry , University of Oxford , Chemistry Research Laboratory , 12 Mansfield Road , Oxford OX1 3TA , UK.
  • Goicoechea JM Department of Chemistry , University of Oxford , Chemistry Research Laboratory , 12 Mansfield Road , Oxford OX1 3TA , UK.
  • 2017-07-19
Published in:
  • Chemical science. - 2015
English 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.
Language
  • English
Open access status
gold
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Persistent URL
https://sonar.ch/global/documents/238246
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