Formation of an iridium σ-cyclopropane complex by the intramolecular activation of a cyclopropylphosphine: Rearrangement to a chelating σ-vinyl complex

Wiley J. Youngs*, Barbara L. Simms, James A Ibers

*Corresponding author for this work

Research output: Contribution to journalArticle

9 Scopus citations


When (t-Bu)2PCH2CHCH2CH2 is combined with [IrCl(C8H14)2]2 in toluene, the σ-bound cyclopropane complexes {A figure is presented}(P(t-Bu)2CH2CHCH2CH2) (1a, 1b) are formed. Complexes 1a,1b react readily with H2 to form IrClH2P(t-Bu)2CH2CHCH2CH2)2 (2). In polar solvents 1a,1b isomerize to the σ-vinyl chelated complex IrClH(P(t-Bu)2CH2C(CH3)CH)(P(t-Bu)2CH2CHCH2CH2) (3). The structure of this 5-coordinate, 16-electron IrIII complex was deduced from spectroscopic data, reaction chemistry, and from the crystal structure of its CO adduct (4). Compound 4 crystallizes in the monoclinic space group C2h5-P21/n (a 15.610(14), b 15.763(16), c 11.973(13) Å, and β 104.74(5)°) with 4 molecules per unit cell. The final agreement indices for 2326 reflections having Fo2 > 3σ(Fo2) are R(F) = 0.089 and Rw(F) = 0.095 (271 variables) while R(F2) is 0.148 for the 3423 unique data. Bond lengths in the 5-atom chelate ring IrPCCC are IrP 2.341(4), PC 1.857(26), CC 1.520(30), CC 1.341(25), and CIr 1.994(21) Å. The IrCl distance is 2.479(5) Å.

Original languageEnglish (US)
Pages (from-to)295-307
Number of pages13
JournalJournal of Organometallic Chemistry
Issue number2
StatePublished - Sep 4 1984


ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this