Gold(I) organosulfinate and organosulfonate complexes

(Phosphine)gold(I) organosulfonates and organosulfinates (R₃P)Au-OS(O)₂R′ (A) and (R₃P)Au-S(O)₂R′ (B), respectively, are active catalysts for the addition of alcohols to alkynes. A series of compounds of type A (R = Ph and Me, R′ = p-Tol; R = Ph, R′ = p-Py; R = Ph and Me, R′ = Et) and type B (R = Ph, R′ = p-Tol; R = Ph and Me, R′ = Me) were prepared and characterized by analytical and spectroscopic data. The crystal structure of [p-TolS(O)₂O-Au(PPh₃)]·CH₂Cl ₂ was determined by single crystal X-ray diffraction. The molecules are aggregated into pairs with O-bonded gold atoms and short Au ··· Au contacts [3.1770(3) Å]. By contrast, crystals of "p-TolS(O)O-Au(PPh₃)" contain intimately aggregated ion pairs of the homoleptic components [(Ph₃P)₂Au]⁺[{p-TolS(O)₂} ₂Au]^- with a short Au ··· Au contact [2.9249(2) Å] and a strongly bent P-Au-P axis [156.66(4)^o]. The sulfinate ligands are both S-bonded to the gold atom. Analogous p-tolylsulfinate complexes were also prepared with the isocyanide ligands ^tBuNC and 2,6-Me₂C₆H₃NC. Their spectroscopic data indicate ionic solid state structures with homoleptic cations and anions.