자료유형  

 학위논문

Control Number  

0016932853

International Standard Book Number  

9798379850531

Dewey Decimal Classification Number  

540

Main Entry-Personal Name  

Rupasinghe, Dissanayake Mudiyanselage Ramitha Yasas Pathmila.

Publication, Distribution, etc. (Imprint  

[S.l.] : Purdue University., 2022

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2022

Physical Description  

1 online resource(161 p.)

General Note  

Source: Dissertations Abstracts International, Volume: 85-01, Section: B.

General Note  

Advisor: Bart, Suzanne C.

Dissertation Note  

Thesis (Ph.D.)--Purdue University, 2022.

Restrictions on Access Note  

This item must not be sold to any third party vendors.

Summary, Etc.  

요약Thorium complexes primarily exist in the thermodynamically stable (IV) oxidation state with only a few low-valent thorium(III) and thorium(II) complexes having been isolated. As a result, redox chemistry with thorium at the metal center is synthetically challenging without carefully selected ligand systems. This redox-restricted nature of thorium(IV) makes redox-active ligands (RALs) an attractive option to facilitate multi-electron redox chemistry with thorium. In this work, first, a series of thorium(IV) complexes featuring the redox-active iminoquinone ligand and its derivatives, including the iminosemiquinone and amidophenolate species, were synthesized and characterized. Rare thorium oxygen multiple bonds were then accessed by exploiting the RALs on the thorium center and using dioxygen in dry air. Other oxidation chemistry was attempted with the thorium amidophenolate complexes as well. Second, armed with the knowledge of synthesizing multiple bonds with thorium(IV) complexes, similar chemistry was explored with cerium as it is in the same group as thorium. A series of cerium(III) and cerium(IV) complexes featuring the redox-active iminoquinone ligand and its derivatives were synthesized. Oxidation chemistry was explored with the cerium amidophenolate complexes and a rare cerium oxo was isolated. Finally, with interest in expanding and addressing a gap in the literature related to the synthesis, characterization, and utility of thorium alkyls, several tetrabenzylthorium complexes were synthesized, characterized, and some reactivity was explored. A highlight of this work involved the isolation of the first crystal structure of ligand and solvent free tetrabenzylthorium since its first synthesis in 1974. Full spectroscopic and structural characterization of the complexes was performed via 1H NMR spectroscopy, X-ray crystallography, EPR spectroscopy, electronic absorption spectroscopy, and SQUID magnetometry, which all confirmed the identity and electronic structure of these complexes.

Subject Added Entry-Topical Term  

Crystal structure.

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Iodine.

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Hydrocarbons.

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Graphite.

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Oxidation.

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Single crystals.

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Nuclear magnetic resonance--NMR.

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Carbon.

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Magnetic fields.

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Solvents.

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Hydrogen.

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Chemistry.

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Chemical bonds.

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Potassium.

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Molecular structure.

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Magnetism.

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Crystallography.

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Nitrogen.

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Electromagnetics.

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Medical imaging.

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Physics.

Added Entry-Corporate Name  

Purdue University.

Host Item Entry  

Dissertations Abstracts International. 85-01B.

Host Item Entry  

Dissertation Abstract International

Electronic Location and Access  

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Control Number  

joongbu:643626