Related Experiment Video
Updated: Jun 5, 2025

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Reactivity Study of the Bis(phosphine)-Stabilized Antimony(I) Cation
Nilanjana Mukherjee1, Vikas Kumar1, Cem B Yildiz2
1Department of Chemistry, Indian Institute of Science Education and Research, Pune, Dr. Homi Bhabha Road, Pashan, Pune 411008 Maharashtra, India.
Abstract:
The 5,6-Bis(diisopropylphosphino)acenaphthene L-stabilized Sb(I) cationic compound [LSb][OTf] (OTf = CF3SO3) 1 possessing two lone pairs of electrons on the Sb(I) center showed nucleophilic behavior toward methyl trifluoromethanesulfonate forming the oxidized product [LSbMe][OTf]2 2 (OTf = CF3SO3). Reaction of compound 1 with Lewis acids such as GaCl3 and AlBr3 led to changes in the counteranions only giving products [LSb][GaCl4] 3 and [LSb][SbBr4] 4, respectively. A metathesis reaction was observed when compound 1 was reacted with PI3. The Sb(I) cation in 1 underwent the metathesis reaction with the P(I) cation, forming the more stable product [LP][OTf] 5. The Sb(I) center in 1 was completely oxidized to Sb(V) by reacting with two equivalents of o-chloranil to give the Bis(phosphine)-stabilized Bis(perchloro catecholato)stibonium cation [L(O2C6Cl4)2Sb][OTf] 6. Both compounds 1 and 6 were employed as proof-of-concept Lewis acid catalysts for the hydrosilylation of p-methyl benzaldehyde. All the compounds were characterized using single-crystal X-ray diffraction analysis, multinuclear nuclear magnetic resonance spectroscopy, mass spectrometry, and absorbance spectroscopy. Density functional theory calculations were performed on the relevant compounds.
Related Concept Videos
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
Preparation and Reactions of Sulfides
Preparation and Reactions of Thiols
SN2 Reaction: Transition State
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
Radical Substitution: Allylic Bromination

