The chemistry of centered hexanuclear zirconium chloride clusters in ionic liquids and other nonaqueous solvents

The chemistry of the centered hexanuclear zirconium halide clusters in solutions is currently under development. In this dissertation, synthetic methods for isolating these clusters as soluble precursor compounds, a systematic investigation of oxidation-reduction properties of these clusters in molten salts, and ligand substitution of the carbon centered zirconium chloride cluster are presented.;Basic ambient-temperature ionic liquids, mixtures of 1-ethyl-3-methylimidazolium chloride (ImCl, in excess) and AlCl3 were utilized to excise the centered clusters from solid state compounds. Soluble cluster compounds Im 5Zr6CCl18·C7H8·2CH 3CN and Im4Zr6CCl18 were isolated. These complete a series of soluble cluster compounds with interstitials: Be, B, C, Mn, and Fe. The B-centered cluster compound, Im5Zr6 BCl18, was one-electron oxidized by ferrocenium tetrafluoroborate, and a 13 CBE cluster compound, Im4Zr6BCl18 was obtained.;The unambiguous speciation of these centered clusters in basic ionic liquids, [(Zr6ZCl12)Cl6]n- (Z = Be, B, C, Mn, Fe), enabled us to systematically investigate and compare cluster redox properties. Our electrochemical results are consistent with the scattered observation of cluster reactivity and demonstrate that the [(Zr 6Z)Cl12]n+ cluster core charges is the dominant determinant of their one-electron reduction potentials.;The coordination chemistry of the carbon centered cluster [(Zr6 C)Cl12]2+ was studied. The compounds Im 4Zr6CCl12(NCS)6 and (pyH+) 3[(Zr6CCl12)Cl5(py)]·6py were structurally characterized. With 13C NMR as a probe for terminal ligand substitution, step by step replacement of terminal chlorides on [(Zr 6CCl12)Cl6]4- was carried out. One substitution product, trans-[(Zr6CCl 12)Cl2(n-Bu3PO)4], was isolated and its structure was characterized by X-ray diffraction.