A molecular loop with interstitial channels in a chiral environment and study of formation of metal-metal bonds in dinickel, dipalladium and dititanium complexes /
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| Format: | Thesis eBook |
| Language: | English |
| Published: |
[College Station, Tex.] :
[Texas A&M University],
[2006]
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| Online Access: | Link to OAK Trust copy |
| Abstract: | This dissertation consists of two independent topics: (1) a molecular loop with interstitial channels in a chiral environment; (2) study of formation of metal-metal bonds in dinickel, dipalladium and dititanium complexes. On the first topic, a study of the reaction products of the interaction of cis-Mo₂(DAniF)₂(CH₃CN)₄²⁺ corner pieces with ortho-, meta- and para- isomers of enatiomerically pure ⁻O₂CCH(CH₃)C₆H₄CH(CH₃)CO₂⁻ dicarboxylate was performed. First, an enantiomerically pure molecular loop based on two dimolybdenum units and two para-dicarboxylate linkers was synthesized and structurally characterized. Similar reactions with isomeric ortho- and meta- dicarboxylate linkers, as well as with some nonchiral ligands, showed that the structure of the obtained products depends on the geometry of the ligand. Meta- dicarboxylate linker favors the formation of the chelated product and ortho- dicarboxylate linker produces the mixture of chelated molecules and loops. On the second topic, an investigation of the formation of metal-metal bonds was performed. Study of the one-electron bond obtained upon oxidation of Ni₂⁴⁺ and Pd₂⁴⁺ toNi₂⁵⁺ and Pd₂⁵⁺, respectively, was made. The compounds synthesized were studied with various physical methods, such as X-ray crystallography, UV-visible spectroscopy and EPR spectroscopy. The nature of oxidized species as well as the dependence of metal-metal interactions on electron-donating abilities of bridging ligands was studied. It was shown that oxidation takes place on a metal center. The formation of one-electron bond in oxidized species is proposed. Finally formation of Ti₂⁶⁺ single bonded compounds by the reduction of two Ti⁴⁺ monomers to Ti₂⁶⁺ dimer was studied. The nature of the species obtained in solution and in solid state is discussed. The crystal structure shows the presence of two types of hpp ligands - chelating and bridging. NMR study of this compound in solution proposes the rearrangement of this structure to a paddlewheel. |
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| Item Description: | "Major Subject: Chemistry" Title from author supplied metadata (automated record created on Sep. 15, 2006.) Vita. Abstract. Electronic resource. |
| Format: | Mode of access: World Wide Web. System requirements: World Wide Web access and Adobe Acrobat Reader. |
| Bibliography: | Includes bibliographical references. |