Crystal and molecular structure of (η3-allyl)carbonylchlorobis(dimethylphenylphosphine)- iridium(III) hexafluorophosphate, [Ir(η3-C3H5)Cl(CO)(P(CH3)2(C6H5))2][PF6

James A. Kaduk*, Arthur T. Poulos, James A. Ibers

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

6 Scopus citations


The structure of (η3-allyl)carbonylchlorobis(dimethylphenylphosphine)-iridium(III) hexafluorophosphate, [Ir(η3-C3H5)Cl(CO)(P(CH3)2(C6H5))2][PF6], has been determined from three-dimensional X-ray data to add support for a proposed mechanism of the oxidative addition of allyl halides to IrX(CO)(PR3)2 (X = halide). The compound crystallizes in space group C52h-P21/c with four formula units in a cell of dimensions a = 11.027(1), b = 12.230(2), c = 19.447(5) Å, and β = 103.16(2)0. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.066 for the 3018 independent reflections having F20>3-(F20). The crystal structure consists of discrete, monomericions. The hexafluorophosphate anion is disordered. The coordination geometry around the iridium atom may be described as octahedral, with the chloro ligand trans to the carbonyl group and each phosphorus atom trans to a terminal carbon of the allyl group. Structural parameters: Ir-P = 2.366(4), 2.347(3);Ir-Cl = 2.389(3); Ir-C(allyl) = 2.28(1), 2.24(1),2.25(1); Ir-C (carbonyl) = 1.85(1) Å; P-Ir-P = 105.7(1); C(terminal)-Ir-C(terminal) = 66.2(8); C-C-C = 125(2)o. The allyl group makes an angle of 126o with the P-Ir-P plane. Correlations between geometric structure and number of d electrons are noted among several M-C3H5-complexes, and are interpreted in the light of theoretical models of the M-C3H5- bond.

Original languageEnglish (US)
Pages (from-to)245-260
Number of pages16
JournalJournal of Organometallic Chemistry
Issue number2
StatePublished - Mar 1 1977

ASJC Scopus subject areas

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


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