The reactions of Na2dmit (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate) with AuClL in 1:2 ratios lead to [Au2(dmit)L2] [L = PPh3 (1), PPh2Me (2), PPhMe2 (3), PMe3 (4), CH2PPh3 (5), CH2PPh2Me (6), CH2PPhMe2 (7)]. Complexes 1, 2, and 5 react further with equimolecular amounts of [AuL(tht)]ClO4 (tht = tetrahydrothiophene), affording trinuclear complexes [Au3(dmit)L3]ClO4 (8−10). When the reactions of Na2dmit with AuClL are carried out in 1:1 ratios and in the presence of NBu4Br, mononuclear tricoordinated gold(I) complexes NBu4[Au(dmit)L] [L = PPh3 (11), PPh2Me (12), PMe3 (13)] are obtained. Other anionic derivatives such as (PPN)2[Au2(dmit)X2] [X = C6F5 (14), Cl (15a), Br (15b)] can be obtained either by reaction of Na2dmit with Q[Au(C6F5)X] in 1:2 ratio or by addition of (PPN)X to the recently reported [Au2(dmit)(AsPh3)]. Oxidative reactions of 11, 12, and 14 or 15b with excess (TTF)3(BF4)2 afford (TTF)2[Au(dmit)2] (16), (TTF)[Au2(dmit)(C6F5)2] (17), and (TTF)3[Au2(dmit)Br2] (18), respectively. Reaction of ...