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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
- 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
- Silicon
- 키워드
- Silylenes
- 기타저자
- University of California, Berkeley Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-03B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520250211152731
■006m o d
■007cr#unu||||||||
■020 ▼a9798384455295
■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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