A variety of new and known transition metal dithiolene complexes has been synthesized from thiometalates via induced internal electron-transfer reactions. Treating MS42- (M = Mo, W) with stoichiometric amounts of bis(trifluoromethyl)-1,2-dithiete ((CF3)(2)C2S2) results in rapid formation of the respective tris(dithiolene) complexes M(tfd)(3)(2-) (tfd = [(CF3)(2)C2S2](2-)). These complexes are isostructural and adopt twisted trigonal prismatic coordination (ca. 18 degrees from a perfect trigonal prism). Crystal data: Mo(tfd)(3)(2-) monoclinic, space group C2/c, with a 18.905(4) Angstrom, b = 13.732(3) Angstrom, c = 17.101(3) Angstrom, beta = 110.29(3)degrees. and Z = 4;W(tfd)(3)(2-), monoclinic, space group C2/c, with a = 18.933(4) Angstrom, b = 13.728(3) Angstrom, c = 17.096(3) Angstrom, beta = 110.26(3)degrees, and Z = 4. In contrast, Mo(tfd)(3) (synthesized as reported previously) has nearly perfect trigonal prismatic coordination. Crystal data: hexagonal, space group P6(3)/m, with a = 9.6795(14) Angstrom, b = 9.6795(14) Angstrom, c = 13.951(3) Angstrom, and Z = 2. Treating WOS32- and MoO2S22- With (CF3)(2)C2S2 results in the respective MO(tfd)(2)(2-) complexes. These two complexes are isostructural and adopt square pyramidal coordination with four sulfur atoms forming the base and oxygen at the apex. Crystal data: MoO(tfd)(2)(2-), monoclinic, space group P2(1)/n, with a = 12.184(2) Angstrom, b = 18.627(4) Angstrom, c = 15.482(3) Angstrom, beta = 91.06(3)degrees, and Z = 4; WO(tfd)(2)(2-) monoclinic, space group P2(1)/n, with a = 12.200(2) Angstrom, b = 18.630(4) Angstrom, c = 15.443(3) Angstrom, beta = 91.02(3)degrees, and Z = 4. On the basis of spectroscopic evidence, the product from the reaction of ReS4- with (CF3)(2)C2S2 is proposed to be {Re[S2C2(CF3)(2)][S3C2(CF3)(2)](2)}(-) Influences of the nature of the oxidant on the ease with which thiometalates undergo induced internal electron-transfer reactions are discussed.