Synthesis and substitution chemistry of clusters containing the {tungsten(6)chlorine(8)}(+4) core

Although the chemistry of clusters containing the {Mo6Cl 8}4+ core has been extensively investigated, that of the heavier tungsten congeners has received considerable less attention. The research described in this dissertation focuses on the preparation of axially substituted clusters of the type [W6Cl8X6] 2-, where X is a halide, pseudohalide, or organometallic ligand. The substitutional lability of the axial sites is enhanced by the incorporation of the weakly coordinating ligands triflate (trifluoromethanesulfonate, -OSO2CF3) and tosylate (p-toluenesulfonate, -OSO2C6H4CH3). The lightly coordinated complexes [Bu4N]2[W6Cl 8(OSO2CF3)6] and [Bu4N] 2[W6Cl8(OSO2C6H4CH 3)6] have been prepared and fully characterized, and have served to generate a variety substituted products. The clusters generated from these materials have been characterized by a variety of spectroscopic, spectrometric, and structural techniques. X-ray crystal structures of these two lightly coordinated clusters, as well as the pseudohalide complexes [Bu 4N]2[W6Cl8(NCQ)6] (Q = O, S, Se), the acetate species [Bu4N]2[W6Cl 8(OC(O)CH3)6], and the fluoride cluster [Bu 4N]2[W6Cl8F6] have been obtained.