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THE SYNTHESIS OF A TRIS(1,4-BUTANEDIYLDITHIOETHYLENE-1,2-DITHIOLATE) COMPLEX OF VANADIUM. STRUCTURE AND ELECTRONIC PROPERTIES

Abstract A monoanionic vanadium complex has been isolated from the reaction of vanadium(III) chloride and the dipotassium salt of the dithiolene, 1,4-butanediyldithioethylene-1,2-dithiolate (BDDT). The complex, isolated as the tetraethylammonium salt and recrystallized from acetone, produced dark blue crystals suitable for an X-ray structural study. The material crystallizes in the monoclinic system, space group P21/c, with a = 10.798(11) A, b = 19.244(30) A, c = 36.370(42) A, β = 92.23(7)°, V = 7552(12) A3, z = 8, and R = 0.1106. Extended Huckel molecular orbital calculations suggest that this is best described as a V(V) complex. In contrast, however, a comparison of the MO calculation with the tris-vanadium complex of 1,2-ethanediyldithioethylene-1,2-dithiolate (DDDT) suggests this latter system is more appropriately described as a lower oxidation state of vanadium with a partially oxidized ligand. The structural data also suggest this interpretation.