Oxidation of the Carbonylbis(1,2-bis(diphenylphosphino)ethane)iridium(I) Cation. Preparation and Characterization of a Series of Iridium(III) Carbonyl Dications

Michael A. Lilga, James A Ibers

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Oxidation of Ir(CO)(dppe)2+ with halogens affords cw-IrX(CO)(dppe)22+ (X = Cl, Br) while oxidation with HBF4affords cis-IrH(CO)(dppe)22+. The species trans-IrX(CO)(dppe)22+ (X = Cl, Br) are prepared by the oxidation of Ir(CO)(dppe)2+ with nitrosonium ion in the presence of Cl- or Br-. The complex transs-IrH(CO)(dppe)22+ is most convenientlyprepared by protonation of [Ir(dppe)2]BF4 with HBF4-Et2O to afford the intermediate IrH(dppe)22+, followedby CO addition. In contrast, both cis-and trans-IrCl(CO)(dppe)22+ species are formed by the electrochemical oxidation of Ir(CO)(dppe)2+ in chloride media. The trans isomer is reduced at a more negative potential and is thus thermodynamically the more stable. Reversible deprotonation of cis-[IrH(CO)(dppe)2][BF4]2 by chloride implies that the acidity of this compound is of the order of that of HC1, unusually strong for a third-row transition-metal hydrido complex.

Original languageEnglish (US)
Pages (from-to)3538-3543
Number of pages6
JournalInorganic chemistry
Issue number22
StatePublished - Jan 1 1984


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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