An Iron-Catalyzed Route to Dewar 1,3,5-Triphosphabenzene and Subsequent Reactivity.
Adam N BarrettMartin DiefenbachMary F MahonVera KrewaldRuth L WebsterPublished in: Angewandte Chemie (International ed. in English) (2022)
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.
Keyphrases
- density functional theory
- room temperature
- visible light
- molecular dynamics
- metal organic framework
- gram negative
- ionic liquid
- electron transfer
- high throughput
- high resolution
- hydrogen peroxide
- reduced graphene oxide
- highly efficient
- atomic force microscopy
- multidrug resistant
- sewage sludge
- carbon dioxide
- risk assessment
- gold nanoparticles
- single cell