The reactions of Na(2)dmit (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate) with AuClL in 1:2 ratios lead to [Au-2(dmit)L(2)] [L = PPh(3) (1), PPh(2)Me (2), PPhMe(2) (3), PMe(3) (4), CH(2)PPh(3) (5), CH(2)PPh(2)Me (6), CH(2)PPhMe(2) (7)]. Complexes 1, 2, and 5 react further with equimolecular amounts of [AuL(tht)]ClO4 (tht = tetrahydrothiophene), affording trinuclear complexes [Au-3(dmit)L(3)]ClO4 (8-10). When the reactions of Na(2)dmit with AuClL are carried out in 1:1 ratios and in the presence of NBu(4)Br, mononuclear tricoordinated gold(I) complexes NBu(4)[Au(dmit)L] [L = PPh(3) (11), PPh(2)Me (12), PMe(3) (13)] are obtained. Other anionic derivatives such as (PPN)(2)[Au-2(dmit)X(2)] [X = C6F5 (14), Cl (15a) Br (15b)] can be obtained either by reaction of Na(2)dmit with Q[Au(C6F5)X] in 1:2 ratio or by addition of (PPN)X to the recently reported [Au-2(dmit)(AsPh(3))]. Oxidative reactions of 11, 12, and 14 or 15b with excess (TTF)(3)(BF4)(2) afford (TTF)(2)[Au(dmit)(2)] (16), (TTF)[Au-2(dmit)(C6F5)(2)] (17), and (TTF)(3)[Au-2(dmit)Br-2] (18), respectively. Reaction of complex 14 with TCNQ gives the anionic gold(III) complex [Au(dmit)(C6F5)(2)](-) (19). Electrical conductivities of these complexes at room temperature in compacted pellets are 2 x 10(-3) (16), 7 x 10(-5) (17), and 2 x 10(-2) (18) S . cm(-1). Electrocrystallization of 1 and 11 affords [Au-2(dmit)(2)(PPh(3))] (20) and the known NBu(4)[Au(dmit)(2)], respectively. X-ray structure determinations were performed for complexes 1, 11, and 19b.