Coupling of terminal alkynes and isonitriles by organoactinide complexes: Scope and mechanistic insights

E. Barnea, T. Andrea, J. C. Berthet, M. Ephritikhine, M. S. Eisen

Research output: Contribution to journalArticlepeer-review

32 Scopus citations

Abstract

The coupling reaction of terminal alkynes with several isonitriles, catalyzed by the neutral organoactinide complexes Cp2*AnMe 2 (Cp* = C5Me5, An = Th, U) or the cationic complex [(Et2N)3U][BPh4], yielded substituted α,β-acetylenic aldimines, in good to excellent yields. The reaction proceeded via a 1,1-insertion of the isonitrile carbon into a metal-acetylide bond, followed by a protonolysis by the acidic proton of the terminal alkyne. Additional insertion products were obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is also presented, based on kinetics measurements and thermodynamic studies of the coupling reaction with Cp2*ThMe2 or [(Et2N)3U][BPh4] as catalysts. The reaction is first-order in catalyst and isonitrile and zero-order in alkyne.

Original languageEnglish
Pages (from-to)3103-3112
Number of pages10
JournalOrganometallics
Volume27
Issue number13
DOIs
StatePublished - 14 Jul 2008
Externally publishedYes

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