SYNTHESES AND SPECTROSCOPIC AND ELECTRICAL-PROPERTIES OF [W(C3S5)(3)](2-) AND [MO(C3S5)(3)](2-) ANION COMPLEXES AND THEIR OXIDIZED SPECIES AND X-RAY CRYSTAL-STRUCTURES OF [NBU(4)(N)](2)[W(C3S5)(3)],[NBU4N](2)[MO(C3S5)(3)], AND [FE(C(5)ME(5))(2)][W(C3S5)(3)]

[NBu(4)(n)](2)[W(C3S5)(3)] (1) and [NBu(4)(n)](2)[MO(C3S5)(3)] (2) [C3S52- = 4,5-dimercapto-1,3-dithiole-2-thionate(2-)] were prepared. Single-crystal X-ray structure analyses revealed a distorted trigonal prismatic coordination around the metal atom for both the anion moieties. They were oxidized by [Fe(C(5)Me(5))(2)] [BF4] to afford [Fe(C(5)Me(5))][W(C3S5)(3)] (3) and [Fe(C(S)Me(5))(2)][MO(C3S5)(3)] (4), respectively. A single-crystal structure analysis of 3 revealed that the complex consists of the [Fe(C(5)Me(5))(2)](+) cation and the [W(C3S5)(3)](-) anion with almost a regular trigonal prismatic geometry around the tungsten atom and that the anion moieties are arranged one-dimensionally through sulfur-sulfur nonbonded contacts in the crystal phase. Complexes 1 and 2 reacted with iodine, [Fe(C5H5)(2)][PF6], or [TTF](3)[BF4](2) (TTF+. = the tetrathiafulvalenium radical cation) to afford oxidized species [NBU4n](x)[M(C3S5)(3)] (M = W, Mo; chi = 0.05-0.4). One-electron-oxidized complexes 3 and 4 exhibit electrical conductivities of 6.0 x 10(-5) and 1.1 x 10(-4) S cm(-1), respectively, and the further oxidized species 1 x (10(-3)-10(-1)) S cm(-1) at room temperature as compacted pellets. Redox potentials of 1 and 2 were determined. Electronic absorption, IR, ESR spectra, and magnetic properties of these tungsten and molybdenum complexes are discussed. Crystal data: 1, orthorhombic, Pca2(1), a = 32.905(7) Angstrom, b = 10.779(2) Angstrom, c = 16.398(3) Angstrom, V = 5816(2) Angstrom(3), Z = 4, 4847 reflections, R = 0.049; 2, orthorhombic, Pca2(1), a = 32.881(1) Angstrom, b = 10.788(5) Angstrom, c = 16.382(9) Angstrom, V = 5811(5) Angstrom(3), Z = 4, 3303 reflections, R = 0.087; 3, triclinic, P (l) over bar, a = 12.150(2) Angstrom, b = 14.756(1) Angstrom, c = 11.9041(9) Angstrom, alpha = 110.771(6)degrees, beta = 97.087(8)degrees, gamma = 83.84(1)degrees, V = 1975.7(4) Angstrom(3), Z = 2, 9578 reflections, R = 0.040.