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Multi-Electron Redox Chemistry with Thorium and Cerium Iminoquinone Complexes to Form Rare Multiple Bonds- [electronic resource]
Multi-Electron Redox Chemistry with Thorium and Cerium Iminoquinone Complexes to Form Rare Multiple Bonds- [electronic resource]
상세정보
- 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.
- Subject Added Entry-Topical Term
- Iodine.
- Subject Added Entry-Topical Term
- Hydrocarbons.
- Subject Added Entry-Topical Term
- Graphite.
- Subject Added Entry-Topical Term
- Oxidation.
- Subject Added Entry-Topical Term
- Single crystals.
- Subject Added Entry-Topical Term
- Nuclear magnetic resonance--NMR.
- Subject Added Entry-Topical Term
- Carbon.
- Subject Added Entry-Topical Term
- Magnetic fields.
- Subject Added Entry-Topical Term
- Solvents.
- Subject Added Entry-Topical Term
- Hydrogen.
- Subject Added Entry-Topical Term
- Chemistry.
- Subject Added Entry-Topical Term
- Chemical bonds.
- Subject Added Entry-Topical Term
- Potassium.
- Subject Added Entry-Topical Term
- Molecular structure.
- Subject Added Entry-Topical Term
- Magnetism.
- Subject Added Entry-Topical Term
- Crystallography.
- Subject Added Entry-Topical Term
- Nitrogen.
- Subject Added Entry-Topical Term
- Electromagnetics.
- Subject Added Entry-Topical Term
- Medical imaging.
- Subject Added Entry-Topical Term
- 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
- 로그인을 한후 보실 수 있는 자료입니다.
- Control Number
- joongbu:643626
MARC
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■006m o d
■007cr#unu||||||||
■020 ▼a9798379850531
■035 ▼a(MiAaPQ)AAI30506386
■035 ▼a(MiAaPQ)Purdue21644666
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a540
■1001 ▼aRupasinghe, Dissanayake Mudiyanselage Ramitha Yasas Pathmila.
■24510▼aMulti-Electron Redox Chemistry with Thorium and Cerium Iminoquinone Complexes to Form Rare Multiple Bonds▼h[electronic resource]
■260 ▼a[S.l.]▼bPurdue University. ▼c2022
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2022
■300 ▼a1 online resource(161 p.)
■500 ▼aSource: Dissertations Abstracts International, Volume: 85-01, Section: B.
■500 ▼aAdvisor: Bart, Suzanne C.
■5021 ▼aThesis (Ph.D.)--Purdue University, 2022.
■506 ▼aThis item must not be sold to any third party vendors.
■520 ▼aThorium 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.
■590 ▼aSchool code: 0183.
■650 4▼aCrystal structure.
■650 4▼aIodine.
■650 4▼aHydrocarbons.
■650 4▼aGraphite.
■650 4▼aOxidation.
■650 4▼aSingle crystals.
■650 4▼aNuclear magnetic resonance--NMR.
■650 4▼aCarbon.
■650 4▼aMagnetic fields.
■650 4▼aSolvents.
■650 4▼aHydrogen.
■650 4▼aChemistry.
■650 4▼aChemical bonds.
■650 4▼aPotassium.
■650 4▼aMolecular structure.
■650 4▼aMagnetism.
■650 4▼aCrystallography.
■650 4▼aNitrogen.
■650 4▼aElectromagnetics.
■650 4▼aMedical imaging.
■650 4▼aPhysics.
■690 ▼a0485
■690 ▼a0607
■690 ▼a0574
■690 ▼a0605
■71020▼aPurdue University.
■7730 ▼tDissertations Abstracts International▼g85-01B.
■773 ▼tDissertation Abstract International
■790 ▼a0183
■791 ▼aPh.D.
■792 ▼a2022
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T16932853▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
■980 ▼a202402▼f2024
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