Insertion of imine into palladium-methyl and palladium-acyl bonds. A density functional study

Luigi Cavallo*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

Abstract

The insertion mechanism of imine into the Pd-methyl and Pd-acyl bonds with a phosphane or a nitrogen-based ligand coordinated to the Pd atom has been studied with density functional theory. In agreement with the experimental findings, σ coordination of the imine is preferred. Imine insertion into the Pd-methyl bond present high energy barriers (>40 kcal mol-1) independently of the Pd-ligand used. On the contrary insertion into the Pd-acyl bond is more facile, with energy barriers close to 20 kcal mol- 1. A geometrical and energetic analysis of the transition states suggests that the formation of the very strong amide linkage constitutes the added driving force for the imine insertion into the Pd-acyl bond.

Original languageEnglish (US)
Pages (from-to)4238-4241
Number of pages4
JournalJournal of the American Chemical Society
Volume121
Issue number17
DOIs
StatePublished - May 5 1999

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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