Competitive C-I versus C-CN reductive elimination from a RhIII complex. Selectivity is controlled by the solvent

Moran Feller, Mark A. Iron, Linda J.W. Shimon, Yael Diskin-Posner, Gregory Leitus, David Milstein

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The RhIII complex [(PNP)Rh(CN)(CH3)][I] 5, obtained by oxidative addition of methyl iodide to [(PNP)Rh(CN)] 2, reacts selectively in two pathways: In aprotic solvents C-I reductive elimination of methyl iodide followed by its electrophilic attack on the cyano ligand takes place, giving the methyl isonitrile RhI complex [(PNP)Rh(CNCH3)][I] 3, while in protic solvents C-C reductive elimination of acetonitrile takes place forming an iodo RhI complex [(PNP)RhI] 9. Reaction of 2 with ethyl iodide in aprotic solvents gave the corresponding isonitrile complex, while in protic solvents no reactivity was observed. The selectivity of this reaction is likely due to a hydrogen bond between the cyano ligand and the protic solvent, as observed by X-ray diffraction, which retards electrophilic attack on this ligand.

Original languageEnglish
Pages (from-to)14374-14375
Number of pages2
JournalJournal of the American Chemical Society
Volume130
Issue number44
DOIs
Publication statusPublished - Nov 5 2008

ASJC Scopus subject areas

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

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