Syntheses of Metal Dithiolene Complexes from Thiometalates by Induced Internal Redox Reactions

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)2C2S2) results in rapid formation of the respective tris(dithiolene) complexes M(tfd)32- (tfd = [(CF3)2C2S2]2-). These complexes are isostructural and adopt twisted trigonal prismatic coordination (ca. 18° from a perfect trigonal prism). Crystal data:  Mo(tfd)32-, monoclinic, space group C2/c, with a = 18.905(4) A, b = 13.732(3) A, c = 17.101(3) A, β = 110.29(3)°, and Z = 4; W(tfd)32-, monoclinic, space group C2/c, with a = 18.933(4) A, b = 13.728(3) A, c = 17.096(3) A, β = 110.26(3)°, and Z = 4. In contrast, Mo(tfd)3 (synthesized as reported previously) has nearly perfect trigonal prismatic coordination. Crystal data:  hexagonal, space group P63/m, with a = 9.6795(14) A, b = 9.6795(14) A, c = 13.951(3) A, and Z = 2. Treating WOS32- and MoO2S22- with (CF3)2...