Synthesis and study of cationic, two-coordinate triphenylphosphine-gold-π complexes.

Journal Article (Journal Article)

Cationic, two-coordinate triphenylphosphine-gold(I)-π complexes of the form [(PPh₃)Au(π ligand)]⁺SbF₆⁻ (π ligand=4-methylstyrene, 1∙SbF₆), 2-methyl-2-butene (3∙SbF₆), 3-hexyne (6∙SbF₆), 1,3-cyclohexadiene (7∙SbF₆), 3-methyl-1,2-butadiene (8∙SbF₆), and 1,7-diphenyl-3,4-heptadiene (10∙SbF₆) were generated in situ from reaction of [(PPh₃)AuCl], AgSbF₆, and π ligand at -78 °C and were characterized by low-temperature, multinuclear NMR spectroscopy without isolation. The π ligands of these complexes were both weakly bound and kinetically labile and underwent facile intermolecular exchange with free ligand (ΔG(≠) ≈9 kcal mol(-1) in the case of 6∙SbF₆) and competitive displacement by weak σ donors, such as trifluoromethane sulfonate. Triphenylphosphine-gold(I)-π complexes were thermally unstable and decomposed above -20 °C to form the bis(triphenylphosphine) gold cation [(PPh₃)₂Au]⁺SbF₆⁻ (2∙SbF₆).

Full Text

Duke Authors

Cited Authors

  • Brooner, REM; Brown, TJ; Widenhoefer, RA

Published Date

  • June 2013

Published In

Volume / Issue

  • 19 / 25

Start / End Page

  • 8276 - 8284

PubMed ID

  • 23592521

Pubmed Central ID

  • 23592521

Electronic International Standard Serial Number (EISSN)

  • 1521-3765

International Standard Serial Number (ISSN)

  • 0947-6539

Digital Object Identifier (DOI)

  • 10.1002/chem.201204564


  • eng