(Phosphine)gold(I) trifluoromethanesulfonates, trifluoroacetates and trichlorothioacetates[hair space]

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Max Preisenberger, Annette Schier and Hubert Schmidbaur


Abstract

Stable, crystalline (phosphine)gold(I) trifluoroacetates of the type (R3P)AuOC(O)CF3 have been prepared in high yield from the corresponding chloro complexes with AgOC(O)CF3 in tetrahydrofuran for R = Me, Ph or o-Tol. The crystal structure of (Me3P)AuOC(O)CF3 features trimers with two short aurophilic Au[hair space][hair space]· · ·[hair space][hair space]Au contacts in an angular Au[hair space][hair space]· · ·[hair space][hair space]Au[hair space][hair space]· · ·[hair space][hair space]Au unit. Trichlorothioacetic acid has been aurated (in high yield) using {[(R3P)Au]3O}+BF4 and NaBF4 in dichloromethane to give equally stable compounds (R3P)AuSC(O)CCl3 with 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 compounds are dimers in the solid state, but association is based on only very long intermolecular Au[hair space][hair space]· · ·[hair space][hair space]S and Au[hair space][hair space]· · ·[hair space][hair space]Cl contacts, respectively. (Triphenylphosphine)gold thioacetate was prepared similarly, but the product is thermally unstable in both the solid and solution state. 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 for the controlled deposition of gold. [Tri(o-tolyl)phosphine]gold chloride was converted into the trifluoromethanesulfonate (triflate) in 95% yield by treatment with AgOS(O)2CF3 in tetrahydrofuran. The crystal structure determination of the CH2Cl2 solvate revealed non-ionic, molecular components [Au–O 2.110(3) Å, S–O–Au 120.4(2)°], which are associated into dimers via hydrogen bonds [O[hair space][hair space]· · ·[hair space][hair space]H–C 170.2°, C–H 0.969 Å, H[hair space][hair space]· · ·[hair space][hair space]O 2.575 Å] with two CH2Cl2 molecules.


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