Reactions of AuCl(tht) (tht) tetrahydrothiophene) with various ylides in equimolar amounts give the complexes [AuCl(ylide)]Xn(n)0, ylide) C(PPh3)2(1a), 4-MeC6H4SO2-CHPPh31b);n)1, X)TfO, ylide)[HC(PPh3)2]+(2)) and [(AuCl)2{Ì-C(PPh3)2}](3) when using a 2:1 molar ratio. The complex 1a reacts (i) with Tl(acac) to give [Au(acac) {C(PPh3)2}](4) and (ii) with terminal alkynes (with or without added Et3N) to give [HC(PPh3)2][Au-(C=CC6H4R-4)Cl] (R)H(5a), CN (5b), OMe (5c), NO2(5d)) instead of the desired complexes[Au(C=CC6H4R-4){C{PPh3}2}]. These complexes (R)H(6a), CN (6b), OMe (6c), NO2(6d),C=CPh (6e)) were prepared by the reaction of [Au(acac){C(PPh3)2}](4) with a large excess of alkynes (ca. 1:25-30). Complex 1b reacts with terminal alkynes in the presence of Et3N differently from 1a, giving the complexes [Au(C=CC6H4R-4){CH(PPh3){S(O)2C6H4Me-4}}](R)H(7a), NC (7b), OMe (7c), NO2(7d), C=CPh (7e)). The reaction of PPN[Au(acac)2]with the phosphonium salt [H2C(PPh3)2](TfO)2or [4-MeC6H4S(O)2CH2PPh3 ]TfO in 1:2 stoichiometry afforded the cationic complex [Au(ylide)2](TfO)n, where the ylide is [HC(PPh3)2]+(n)3,8a) or 4-MeC6H4S(O)2CHPPh3(n)1,8b), respectively. The crystal structures of [4-MeC6H4S(O)2CH2PPh3]TfO,1b‚0.5CH2Cl2,3‚3C2Cl2,5a,5c,6d‚THF, and 8b have been determined.