Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 19, Issue 25, Pages 8276-8284Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201204564
Keywords
alkene ligands; allenes; diene ligands; gold; complexes
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Funding
- NSF [CHE-0555425]
- Duke University
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1213957] Funding Source: National Science Foundation
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Cationic, two-coordinate triphenylphosphine-gold(I)-complexes of the form [(PPh3)Au(ligand)]+ SbF6- (ligand=4-methylstyrene, 1SbF6), 2-methyl-2-butene (3SbF6), 3-hexyne (6SbF6), 1,3-cyclohexadiene (7SbF6), 3-methyl-1,2-butadiene (8SbF6), and 1,7-diphenyl-3,4-heptadiene (10SbF6) were generated in situ from reaction of [(PPh3)AuCl], AgSbF6, and ligand at -78 degrees C and were characterized by low-temperature, multinuclear NMR spectroscopy without isolation. The ligands of these complexes were both weakly bound and kinetically labile and underwent facile intermolecular exchange with free ligand (G approximate to 9kcalmol-1 in the case of 6SbF6) and competitive displacement by weak sigma donors, such as trifluoromethane sulfonate. Triphenylphosphine-gold(I)-complexes were thermally unstable and decomposed above -20 degrees C to form the bis(triphenylphosphine) gold cation [(PPh3)2Au]+SbF6- (2SbF6).
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