Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species

Laurence John Taylor, Michael Buehl, Piotr Wawrzyniak, Brian Alexander Chalmers, J Derek Woollins, Alexandra Martha Zoya Slawin, Amy Fuller, Petr Kilian

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)
20 Downloads (Pure)

Abstract

Treatment of Acenap(PiPr2)(EH2) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph3C·BF4 resulted in hydride abstraction to give [Acenap(PiPr2)(EH)][BF4] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low co-ordinate species Acenap(PiPr2)(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ4-phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ4-phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism.

Original languageEnglish
JournalEuropean Journal of Inorganic Chemistry
VolumeEarly view
Early online date6 Oct 2015
DOIs
Publication statusPublished - 2015

Keywords

  • Phosphorus
  • Arsenic
  • Low co-ordinate
  • Peri-substitution
  • Base-stabilisation

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