The reactions of anhydrous gold() chloride [AuCl 3 ] 2 with aromatic hydrocarbons (ArH) such as benzene, toluene, xylenes, mesitylene, cumene, methoxybenzene and chlorobenzene, and the following treatment with 2,6-lutidine (lut) gave stable arylgold() complexes [AuArCl 2 (lut)]. These auration reactions proceeded heterogeneously in hexane and homogeneously in diethyl ether. The 1 H NMR spectra of the arylgold() complexes revealed that aurations towards aromatic compounds take place regiospecifically at the position with higher electron density and with less steric hindrances. The trans configuration of the arylgold() complexes was established by means of their far-IR spectra and confirmed for [Au(2,5-Me 2 C 6 H 3 )Cl 2 (lut)] by its single-crystal X-ray structure. The reactions of [AuArCl 2 (lut)] (Ar = phenyl, 2,5-xylyl) with a terminal alkyne, phenyacetylene (HC᎐ ᎐ ᎐ CPh), afforded arylated phenylacetylenes ArC᎐ ᎐ ᎐ CPh.

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I. It consists of a unique zigzag chain structure in which the distorted [(C3H7)2NCS2T1]2 dimers are connected by interdimer Tl-S linkages such that one T1(I) is six-coordinate while the other is five-coordinate. Instead of an eight-membered ring, it exists as a distorted bipyramid with T1(I) atoms at the apices.Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research.Registry No. [Au(S2CN(C2H5)2)SCN]2, 79255-13-3; [Au(S2C-N(C2H5)2)2][Au(SCN)2], [Au(S2CN(C2H5)2)SeCN]2, 79255-15-5; [Au(S2CN(C2H5)2)2][Au(SeCN)2], 2)Br]2, 79255-18-8; [Au(S2CN(C2H5)2)2][AuBr2], 33916-73-3; [Au(S2CN(C2H5)2)I]2, 79255-19-9; [Au(S2CN(C2-H5)2)2][AuI2], 79255-20-2; [Au(S2CN(C2H5)2)2][Au(SCN)2Br2], 79255-22-4; [Au(S2CN(C4H,)2)SCN]2, 79255-23-5; [Au(S2CN-(C4H9)2)2][Au(SCN)2], [Ag(S2CN(C2H5)2)]6, 59859-16-4; [Au(S2CN(C2H5)2)]2, 66712-10-5; [Au(S2CN(C4H9)2)]2, 59306-90-0; (SCN)2, 505-14-6; (SeCN)2,27151-67-3; Br2, 7726-95-6; I2, 7553-56-2.