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Updated: Oct 9, 2025
Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Reduction of tert-butylphosphaalkyne and trimethylsilylnitrile with magnesium(I) dimers
Daniel W N Wilson1, Dafydd D L Jones2, Cory D Smith2
1Department of Chemistry, University of Oxford, 12 Mansfield Rd, Oxford OX1 3TA, UK. jose.goicoechea@chem.ox.ac.uk.
Abstract:
We report on the reactivity of magnesium(I) dimers, [Mg(nacnac)]2 (nacnac = HC[C(Me)N(2,6-iPr2C6H3)]2 ([DippLMg]2) and HC[C(Me)N(2,4,6-Me3C6H2)]2 ([MesLMg]2)), towards the phosphaalkyne BuCP. The steric profile of the magnesium(I) dimer results in selectivity for different products. The larger diisopropylphenyl derivative yields exclusively the monomeric dimagnesiated phosphaalkene [DippLMg]PC(Bu)([DippLMg]) (1), while the mesityl derivative facilitates reductive coupling of two phosphaalkyne equivalents to give access to the 1,3-diphosphacyclobutadienediide [MesLMg]2[(Bu)2C2P2](2). The reactivity differs in coordinating solvents such as THF, which allowed for the observation of C-P coupled products. For sake of comparison, reactions of magnesium(I) compounds with Me3SiCN were carried out. In contrast to the reactions involving BuCP, these afforded 1,3-diazabutadienediyl complexes via reductive coupling and silyl migration processes.
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