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Updated: Sep 4, 2025

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
An Iron-Catalyzed Route to Dewar 1,3,5-Triphosphabenzene and Subsequent Reactivity
Adam N Barrett1, Martin Diefenbach2, Mary F Mahon1
1Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
Abstract:
The application of an alkyne cyclotrimerization regime with an [Fe(salen)]2 -μ-oxo (1) catalyst to triphenylmethylphosphaalkyne (2) yields gram-scale quantities of 2,4,6-tris(triphenylmethyl)-Dewar-1,3,5-triphosphabenzene (3). Bulky lithium salt LiHMDS facilitates a rearrangement of 3 to the 1,3,5-triphosphabenzene valence isomer (3'), which subsequently undergoes an intriguing phosphorus migration reaction to form the ring-contracted species (3''). Density functional theory calculations provide a plausible mechanism for this rearrangement. Given the stability of 3, a diverse array of unprecedented transformations was investigated. We report novel crystallographically characterized products of successful nucleophilic/electrophilic addition and protonation/oxidation reactions.
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