(Phosphine)gold(I) trifluoromethanesulfonates, trifluoroacetates and trichlorothioacetates

Stable, crystalline (phosphine)gold(I) trifluoroacetates of the type (R3P)A uOC(O)CF3 have been prepared in high yield from the corresponding chloro co mplexes with AgOC(O)CF3 in tetrahydrofuran for R = Me, Ph or o-Tol. The cry stal structure of (Me3P)AuOC(O)CF3 features trimers with two short aurophil ic Au ... Au contacts in an angular Au ... Au ... Au unit. Trichlorothioace tic acid has been aurated (in high yield) using ([(R3P)Au](3)O)+BF4- and Na BF4 in dichloromethane to give equally stable compounds (R3P)AuSC(O)CCl3 wi th R = Me, Ph or o-Tol. In these products the trichlorothioacetate group is exclusively sulfur bonded to the gold atom. The methyl and o-tolyl compoun ds are dimers in the solid slate, but association is based on only very lon g intermolecular Au ... S and Au ... Cl contacts, respectively. (Triphenylp hosphine)gold thioacetate was prepared similarly, but the product is therma lly unstable in both the solid and solution slate. It thus appears that the presence of the halogen substituents is essential for the stability of the present compounds, which are useful aurating agents and can be employed fo r the controlled deposition of gold. [Tri(o-tolyl)phosphine]gold chloride w as converted into the trifluoromethanesulfonate (triflate) in 95% yield by treatment with AgOS(O)(2)CF3 in tetrahydrofuran. The crystal structure dete rmination of the CH2Cl2 solvate revealed non-ionic, molecular components [A u-O 2.110(3) Angstrom, S-O-Au 120.4(2)degrees], which are associated into d imers via hydrogen bonds [O ... H-C 170.2 degrees, C-H 0.969 Angstrom, H .. . O 2.575 Angstrom] with two CH2Cl2 molecules.