Synthesis, Properties, and Crystal Structures of Benzene-1,2-dithiolato Complexes of Thallium(I) and -(III)

The syntheses, molecular structures and properties of homoleptic 1,2-S(2)C(6)H(4) complexes of thallium(I) and thallium(III) with four-coordinated metal centers are described. Anaerobic treatment of TlCl, TlNO(3), or Tl(2)CO(3) with solutions of sodium methanolate and 1,2-(HS)(2)C(6)H(4) in methanol gave after metathesis with NEt(4)]Br yellow solutions of NEt(4)](2){Tl(1,2-(&mgr;-S)(2)C(6)H(4))}(2)] (NEt(4)](2)1). Yellow single crystals were obtained from saturated acetone solutions at -10 degrees C and the crystal data for NEt(4)](2)1 are monoclinic, P2(1)/c, with Z = 2, a = 7.440(1) ?, b = 16.373(3) ?, c = 13.201(2) ?, and beta = 97.08(1) degrees. Complex 1(2)(-)(), the first structurally characterized homoleptic ionic thiolate complex of thallium(I), contains rectangular bipyramidal TlS(4)Tl] cages with the four sulfur atoms defining the equatorial plane and the two thallium atoms in axial positions. The S(2)C(6)H(4) fragments are almost coplanar with the S(4) plane. In the crystal lattice, nearly linear Tl.Tl chains align along the a-axis (offset ca. 3.0 degrees ) with the ligand planes parallel to the bc-plane. Within and between dimers short Tl.Tl distances are observed (Tl.Tl' within a dimeric unit, 3.5116(4) ?; Tl.Tl between dimeric units, 3.9371(3) ?) with the distance between dimeric units being the shortest contact between anions-Tl.S distances between dimeric units are longer than 5.8 ?. Aerobic treatment of TlCl, TlNO(3), or Tl(2)CO(3) with solutions of sodium methanolate and 1,2-(HS)(2)C(6)H(4) in methanol and metathesis with NEt(4)]Br led to NEt(4)]Tl(1,2-S(2)C(6)H(4))(2)] (NEt(4)]2). Yellow single crystals were obtained from saturated acetone solutions at 0 degrees C and the crystal data for NEt(4)]2 are orthorhombic, Pnn2, with Z = 2, a = 11.449(2) ?, b = 10.060(2) ?, c = 9.950(2) ?. Complex 2(-) is the first homoleptic four-coordinate thiolate of thallium(III) and contains the unusually short Tl-S distance of 2.469(4) ?. In solution, ion pairing results in chemical and magnetic inequivalence of the S(2)C(6)H(4) ligands. Although both preparations employ the reaction of thallium(I) salts with 1,2-(NaS)(2)C(6)H(4) in a 1:2 stoichiometry, complex 1(2)(-) is probably not an intermediate to the formation of 2(-). Exposing anaerobically prepared solutions of 1(2)(-) to air results in a series of color changes in the solution over a 20 min period; however, 2(-) could not be observed by NMR spectroscopy.