In order to generate active cationic Au(I) species for homogeneous gold catalysis, silver salts are routinely used in combination with gold chloride complexes. Our observations during the synthesis of gold(I)-enol ether complexes indicated that the expected 'quantitative precipitation of AgCl,' as described throughout the literature, was unreliable. Even though the first filtration through Celite was applied to solutions of (t-Bu)2(o-biphenyl)PAuCl or (t-Bu)3PAuCl with AgSbF6, the filtrate was found to still contain a considerable amount of silver. From these observations and our effort to further probe the phenomena, we report on three new structures: a novel trimetallic silver chloronium complex [(t-Bu)2(o-biphenyl)PAu]2ClAg(SbF6)2 (1 ) and two monomeric digold chloronium complexes, [(t-Bu)2(o-biphenyl)PAu]2ClSbF6 (2) , [(t-Bu)3PAu]2ClSbF6 (3 ). Analyses by X-ray crystallography, NMR spectroscopy, UV absorption and DFT calculation show that for complex 1 , silver displays a significant interaction with biphenyl rings of the phosphine ligand.  Thermodynamic study of 2  and preliminary reactivity of 1, 2  will be presented.

Ligand-silver interaction in a homogeneous gold(I) catalyst

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.