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

28 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

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Ligands
Iodides
Acetonitrile
X-Ray Diffraction
Hydrogen
Hydrogen bonds
X ray diffraction
methyl iodide
acetonitrile

ASJC Scopus subject areas

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

Cite this

Competitive C-I versus C-CN reductive elimination from a RhIII complex. Selectivity is controlled by the solvent. / Feller, Moran; Iron, Mark A.; Shimon, Linda J W; Diskin-Posner, Yael; Leitus, Gregory; Milstein, David.

In: Journal of the American Chemical Society, Vol. 130, No. 44, 05.11.2008, p. 14374-14375.

Research output: Contribution to journalArticle

Feller, Moran ; Iron, Mark A. ; Shimon, Linda J W ; Diskin-Posner, Yael ; Leitus, Gregory ; Milstein, David. / Competitive C-I versus C-CN reductive elimination from a RhIII complex. Selectivity is controlled by the solvent. In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 44. pp. 14374-14375.
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