New Insights in Frustrated Lewis Pair Chemistry with Azides

Devin H.A. Boom, Andrew R. Jupp, Martin Nieger, Andreas W. Ehlers, J. Chris Slootweg*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.

Original languageEnglish
Pages (from-to)13299-13308
Number of pages10
JournalChemistry - A European Journal
Volume25
Issue number58
DOIs
Publication statusPublished - 17 Oct 2019
Externally publishedYes

Keywords

  • azides
  • density functional calculations
  • frustrated Lewis pairs
  • heterocycles
  • isocyanates

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