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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]

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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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■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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