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 mol...
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| Format: | Thesis Book |
| Language: | English |
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[Place of publication not identified] :
[publisher not identified] ;
2000.
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| Subjects: | |
| Online Access: | http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=728416201&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD |
| Summary: | 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 Im₅Zr₆CCl₁₈·C₇H₈·2CH₃CN 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, Im₅Zr₆CCl₁₈, 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][]⁻ (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 [(Zr₆Z)Cl₁₂][]⁺ cluster core charges is the dominant determinant of their one-electron reduction potentials. The coordination chemistry of the carbon centered cluster [(Zr₆C)Cl₁₂]²⁺ was studied. The compounds Im₄Zr₆CCl₁₂(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 [(Zr₆CCl₁₂)Cl₆]⁴⁻ was carried out. One substitution product, trans-[(Zr₆CCl₁₂)Cl₂(n-Bu₃PO)₄], was isolated and its structure was characterized by X-ray diffraction. |
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| Item Description: | Vita. "Major Subject: Chemistry". |
| Physical Description: | xii, 139 leaves : illustrations ; 28 cm. Issued also on microfiche from University Microfilm Inc. |
| Bibliography: | Includes bibliographical references (leaves 99-106). |