Gold(I) organosulfinate and organosulfonate complexes

(Phosphine)gold(t) organosulfonates and organosulfinates (R3P)Au-OS(O)(2)R' (A) and (R3P)Au-S(O)(2)R' (B), respectively, are active catalysts for the addition of alcohols to alkynes. A series of compounds of type A (R = Ph an d 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 b y analytical and spectroscopic data. The crystal structure of [p-TolS(O)(2) O-Au(PPh3)]. CH2Cl2 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) Angstrom]. By contrast. crystals of "p-TolS(O) O-Au(PPh3)" contain intimately aggregated ion pairs of the homoleptic compo nents [(Ph3P)(2)Au](+)[{p-TolS(O)(2)}(2)Au](-) with a short Au . . . Au con tact [2.9249(2) Angstrom] and a strongly bent P-Au-P axis [156.66(4)degrees ]. The sulfinate ligands are both S-bonded to the gold atom. Analogous p-to lylsulfinate complexes were also prepared with the isocyanide ligands (BuNC )-Bu-t and 2,6-Me2C6H3NC. Their spectroscopic data indicate ionic solid sta te structures with homoleptic cations and anions.