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Chiral Phosphine Ligands in the Structural Chemistry of Gold

  • Angela Bayler , Andreas Bauer and Hubert Schmidbaur

Abstract

The reaction of chloro(dimethylsulfide)gold(I) with (2-hydroxybutyl)diphenylphosphine (L) (racemic mixture) in dichloromethane affords high yields of the racemic chiral complex (L)AuCl. Metathesis reactions with KBr or KI, respectively, in a two-phase solvent mix­ ture (CH2CI2/H2O) lead to a conversion into the corresponding bromide and iodide complexes (L)AuBr and (L)AuI. Treatment of silver chloride with the ligand L in acetonitrile yields the analogous 1:1 adduct (L)AgCl. The compounds have been characterized by their analytical and spectroscopic data, and the structures of (L)AuCl and (L)AuBr have been determined by single-crystal X-ray diffraction. The compounds build isomorphous crystal lattices (monoclinic, P21/c) in which pairs of enantiomers (R-and S-configuration of L) are aggregated by two long hydrogen bonds between the hydroxyl group of the ligand and the halogen substituent of the neighbouring molecule. Cationic, linear two-coordinate 1:2 complexes (L)2Au+ X-(X = BF4, CIO4, SO3CF3) and (L)2Ag+ X-(X = BF4) are obtained in good yields by reaction of L with Me2SAuCl and AgX (molar ratio 2:1:1) or with AgBF4 (molar ratio 2:1), respectively. 31P NMR studies at variable temperature show an equilibrium between all possible stereoisomers (RR, SS, RS, SR) in solution with rapid ligand exchange at ambient temperatures.

Received: 1997-10-14
Published Online: 2014-6-2
Published in Print: 1997-12-1

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

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