Specific Photochemical Dehydrocoupling of N-Heterocyclic Phosphanes and Their Use in the Photocatalytic Generation of Dihydrogen

Oliver Puntigam, Lászlõ Könczöl, L. Nyulászi, Dietrich Gudat

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

N-Heterocyclic phosphanes react under UV irradiation in a highly selective dehydrocoupling reaction to diphosphanes and H2. Computational studies suggest that the product formation is initiated by the formation of dimeric molecular associates whose electronic excitation yields H2 and a diphosphane. Combining the dehydrocoupling of sterically demanding phosphanes with Mg-rDEUction of the formed diphosphanes allows constructing a reaction cycle for the photocatalytic rDEUctive generation of H2 from Et3NH+. Hydrogen cycle: Highly selective photochemical dehydrocoupling converts N-heterocyclic phosphanes to diphosphanes and H2, and is a key step in a reaction cycle enabling photocatalytic rDEUctive generation of H2 from Et3NH+. Computational studies suggest that the reaction is initiated by the formation of dimeric molecular associates whose electronic excitation yields H2 and two phosphanyl radicals.

Original languageEnglish
Pages (from-to)11567-11571
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number39
DOIs
Publication statusPublished - Sep 1 2015

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phosphine
Irradiation
Hydrogen

Keywords

  • computational studies
  • dehydrocoupling
  • hydrogen
  • N-heterocyclic phosphanes
  • photolysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

Specific Photochemical Dehydrocoupling of N-Heterocyclic Phosphanes and Their Use in the Photocatalytic Generation of Dihydrogen. / Puntigam, Oliver; Könczöl, Lászlõ; Nyulászi, L.; Gudat, Dietrich.

In: Angewandte Chemie - International Edition, Vol. 54, No. 39, 01.09.2015, p. 11567-11571.

Research output: Contribution to journalArticle

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