Synthesis, Characterization, and Reaction Chemistry of Iridium and Rhodium Cyclopropyl Complexes

Nancy L. Jones, James A Ibers

Research output: Contribution to journalArticle

7 Scopus citations

Abstract

The complexes MCl2(COC3H5)(PMePh2)2, 1 and 7 (M = Ir, Rh), IrCl2(C3H5)(CO)(PMePh2)2, 2 and 3, and IrCl2(COC3H5)(PMePh2)3,5, have been synthesized in good yield by the reaction of cyclopropylmethanoic chloride (C3H5C0C1) with the low-valent coordinatively unsaturated metal complexes [IrC((C8H4)2]2 or [RhCl(C2H4)2]2 after treatment of the latter with PMePh2. Their structures have been deduced by interpretation of 31P{1H) and 1H NMR and IR spectra. In the five-coordinate acyl complexes 1 and 7, the geometry about the metal is square pyramidal with cis phosphine ligands, cis chloro ligands, and an apical cyclopropylmethanoyl ligand. The six-coordinate octahedral bis(phosphine)iridium complexes 2 and 3 contain cis or trans phosphine ligands, respectively, while the tris(phosphine) complex 5 has meridional phosphine ligands. Abstraction of a chloro ligand from IrCl2(COC3H6)(PMePh2)3 by NH4PF6 affords [IrCl(C3H5)(CO)(PMePh2)3][PF6], Reduction of IrCl2(C3H6)(CO)(PMePh2)2,3, by K/benzophenone affords trans-Ir(C3H5)(CO)(PMePh2)2. No evidence for rearrangement of the cyclopropyl group to a π-allyl group is found.

Original languageEnglish (US)
Pages (from-to)490-494
Number of pages5
JournalOrganometallics
Volume2
Issue number4
DOIs
StatePublished - Jan 1 1983

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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