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Updated: Jun 7, 2025

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Sb-to-P Metathesis: A Direct Route to Structurally Constrained, Cationic PIII Compound
Deependra Bawari1, Irina Malahov1, Roman Dobrovetsky1
1School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University, 69978, Tel Aviv, Israel.
Abstract:
Structurally constrained, cationic PIII compound [LP][SbCl4] with an OCO pincer-type ligand (L) having a central carbene donor was directly synthesized via an Sb-to-P metathesis reaction between PCl3 and LSb-Cl. [LP][SbCl4] was isolated and its reactivity with small molecules (ROH and RNH2) was studied, showing that [SbCl4]- is not an innocent counter anion, but an active participant in these reactions. When the [SbCl4]- was replaced with the [CB11H12]- ([Cb]-) anion, the reactions were redirected to [LP]+ cation only. The reactions with alcohols and amines led to the equilibrium between the products of the formal E-H (E=O, N) bond oxidative addition to the P-center and products of the P-center/ligand-assisted bond activation. Remarkably, [LP]+ activated the PhO-H and PhN(H)-H bonds in a reversible, thermoneutral fashion.
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