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Structure and Reactivity of Group 14-Heavy Element Lewis Adducts
Structure and Reactivity of Group 14-Heavy Element Lewis Adducts
Structure and Reactivity of Group 14-Heavy Element Lewis Adducts

Detailed Information

자료유형  
 학위논문 서양
최종처리일시  
20250211152731
ISBN  
9798384455295
DDC  
546
저자명  
Brackbill, I. Joseph.
서명/저자  
Structure and Reactivity of Group 14-Heavy Element Lewis Adducts
발행사항  
[Sl] : University of California, Berkeley, 2024
발행사항  
Ann Arbor : ProQuest Dissertations & Theses, 2024
형태사항  
89 p
주기사항  
Source: Dissertations Abstracts International, Volume: 86-03, Section: B.
주기사항  
Advisor: Arnold, John;Abergel, Rebecca J.
학위논문주기  
Thesis (Ph.D.)--University of California, Berkeley, 2024.
초록/해제  
요약Chapter 1. The relevant background to the project is communicated in addition to the project hypothesis and strategy. Tetrylene-f-element bonded complexes are introduced as compounds of nearly unexplored chemical reactivity and bonding character. The strategy of combining tetrylenes with coordinatively unsaturated f-element precursors is briefly described.Chapter 2. Novel uranium-tetrylene bonded complexes are synthesized by utilization of amidinate-supported silylenes. The solid- and solution-state structures of these compounds are examined by X-ray crystallography, absorption spectroscopy, nuclear magnetic resonance spectroscopy, and variable-temperature magnetometry. The nature of the uranium-silicon interactions is further elucidated by density functional theory methods.Chapter 3. The reactivity of f-element-silylene complexes toward hydrogen gas is reported. Despite showing little evidence for bonding in solution, a uranium-silylene complex rapidly activates hydrogen to yield a dihydrosilane product. Lanthanide analogues to the uranium-silylene complex are much less efficient catalysts, while common main group Lewis acids show no catalytic activity. The mechanisms of both the actinide- and lanthanide-catalyzed reactions are deconvoluted through isotope labeling studies and kinetic and theoretical modeling. Investigation of the uranium-catalyzed pathway reveals that dihydrogen complexation by uranium is accessible and may underpin the particular efficiency of this catalyst.
일반주제명  
Inorganic chemistry
일반주제명  
Physical chemistry
일반주제명  
Materials science
일반주제명  
Analytical chemistry
키워드  
Actinides
키워드  
Dihydrogen complex
키워드  
Low-valent complexes
키워드  
Silicon
키워드  
Silylenes
기타저자  
University of California, Berkeley Chemistry
기본자료저록  
Dissertations Abstracts International. 86-03B.
전자적 위치 및 접속  
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■035    ▼a(MiAaPQ)AAI31490886
■040    ▼aMiAaPQ▼cMiAaPQ
■0820  ▼a546
■1001  ▼aBrackbill,  I.  Joseph.
■24510▼aStructure  and  Reactivity  of  Group  14-Heavy  Element  Lewis  Adducts
■260    ▼a[Sl]▼bUniversity  of  California,  Berkeley▼c2024
■260  1▼aAnn  Arbor▼bProQuest  Dissertations  &  Theses▼c2024
■300    ▼a89  p
■500    ▼aSource:  Dissertations  Abstracts  International,  Volume:  86-03,  Section:  B.
■500    ▼aAdvisor:  Arnold,  John;Abergel,  Rebecca  J.
■5021  ▼aThesis  (Ph.D.)--University  of  California,  Berkeley,  2024.
■520    ▼aChapter  1.  The  relevant  background  to  the  project  is  communicated  in  addition  to  the  project  hypothesis  and  strategy.  Tetrylene-f-element  bonded  complexes  are  introduced  as  compounds  of  nearly  unexplored  chemical  reactivity  and  bonding  character.  The  strategy  of  combining  tetrylenes  with  coordinatively  unsaturated  f-element  precursors  is  briefly  described.Chapter  2.  Novel  uranium-tetrylene  bonded  complexes  are  synthesized  by  utilization  of  amidinate-supported  silylenes.  The  solid-  and  solution-state  structures  of  these  compounds  are  examined  by  X-ray  crystallography,  absorption  spectroscopy,  nuclear  magnetic  resonance  spectroscopy,  and  variable-temperature  magnetometry.  The  nature  of  the  uranium-silicon  interactions  is  further  elucidated  by  density  functional  theory  methods.Chapter  3.  The  reactivity  of  f-element-silylene  complexes  toward  hydrogen  gas  is  reported.  Despite  showing  little  evidence  for  bonding  in  solution,  a  uranium-silylene  complex  rapidly  activates  hydrogen  to  yield  a  dihydrosilane  product.  Lanthanide  analogues  to  the  uranium-silylene  complex  are  much  less  efficient  catalysts,  while  common  main  group  Lewis  acids  show  no  catalytic  activity.  The  mechanisms  of  both  the  actinide-  and  lanthanide-catalyzed  reactions  are  deconvoluted  through  isotope  labeling  studies  and  kinetic  and  theoretical  modeling.  Investigation  of  the  uranium-catalyzed  pathway  reveals  that  dihydrogen  complexation  by  uranium  is  accessible  and  may  underpin  the  particular  efficiency  of  this  catalyst.
■590    ▼aSchool  code:  0028.
■650  4▼aInorganic  chemistry
■650  4▼aPhysical  chemistry
■650  4▼aMaterials  science
■650  4▼aAnalytical  chemistry
■653    ▼aActinides
■653    ▼aDihydrogen  complex
■653    ▼aLow-valent  complexes
■653    ▼aSilicon
■653    ▼aSilylenes
■690    ▼a0488
■690    ▼a0486
■690    ▼a0794
■690    ▼a0494
■71020▼aUniversity  of  California,  Berkeley▼bChemistry.
■7730  ▼tDissertations  Abstracts  International▼g86-03B.
■790    ▼a0028
■791    ▼aPh.D.
■792    ▼a2024
■793    ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17163612▼nKERIS▼z이  자료의  원문은  한국교육학술정보원에서  제공합니다.

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