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Updated: Jun 16, 2025

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Reactivity of the phosphaethynolate anion with stabilized carbocations: mechanistic studies and synthetic
Thi Hong Van Nguyen1, Saloua Chelli1, Sonia Mallet-Ladeira2
1CNRS, Université Paul Sabatier, Laboratoire Hetérochimie Fondamentale et Appliquée (LHFA, UMR5069) 118 Route de Narbonne 31062 Cedex 09 Toulouse France sami.lakhdar@univ-tlse3.fr.
Abstract:
The reactivity of sodium phosphaethynolate Na(OCP) towards various Mayr's reference electrophiles was investigated using conventional UV-visible and laser-flash photolysis techniques. The kinetic data, along with density functional theory (DFT) calculations, enabled the first experimental quantification of the phosphorus nucleophilicity of [OCP]-. Product studies of these reactions demonstrate the formation of secondary as well as tertiary phosphines. The mechanism of this unprecedented phosphorus-atom transfer reaction is thoroughly discussed, with key intermediates successfully isolated and characterized. Importantly, some bulky secondary phosphine oxides synthesized using this approach, have demonstrated high efficiency as ligands in the Suzuki coupling reaction.
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