Reduction of tert -butylphosphaalkyne and trimethylsilylnitrile with magnesium(i) dimers

Daniel W.N. Wilson, Dafydd D.L. Jones, Cory D. Smith, Meera Mehta, Cameron Jones, Jose M. Goicoechea

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2 Citations (Scopus)


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 tBuCP. 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(tBu)([DippLMg]) (1), while the mesityl derivative facilitates reductive coupling of two phosphaalkyne equivalents to give access to the 1,3-diphosphacyclobutadienediide [MesLMg]2[(tBu)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 tBuCP, these afforded 1,3-diazabutadienediyl complexes via reductive coupling and silyl migration processes.

Original languageEnglish
Pages (from-to)898-903
Number of pages6
JournalDalton Transactions
Issue number3
Publication statusPublished - 21 Jan 2022

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