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Catalytic Nitrene Reactions Enabled by Dinuclear Nickel Catalysts- [electronic resource]
Catalytic Nitrene Reactions Enabled by Dinuclear Nickel Catalysts- [electronic resource]
상세정보
- 자료유형
- 학위논문
- Control Number
- 0016932639
- International Standard Book Number
- 9798379832261
- Dewey Decimal Classification Number
- 551.5
- Main Entry-Personal Name
- Andjaba, John M.
- Publication, Distribution, etc. (Imprint
- [S.l.] : Purdue University., 2021
- Publication, Distribution, etc. (Imprint
- Ann Arbor : ProQuest Dissertations & Theses, 2021
- Physical Description
- 1 online resource(513 p.)
- General Note
- Source: Dissertations Abstracts International, Volume: 85-01, Section: B.
- General Note
- Advisor: Uyeda, Christopher.
- Dissertation Note
- Thesis (Ph.D.)--Purdue University, 2021.
- Restrictions on Access Note
- This item must not be sold to any third party vendors.
- Summary, Etc.
- 요약Nitrenes are reactive intermediates that are known to generate high interest organic molecules. Due to their inherent instability, nitrenes are often stabilized by introducing them to transition metal complexes. Many transition metal stabilized nitrenes (M=NR2) have been reported and some of these complexes have been shown to control nitrene reactivity and selectivity. Transition metal nitrene reactivity can be categorized into two main groups: bond-insertion and group transfer reactions. In the reference to the former, chapter one of this dissertation highlights using unique dinuclear Ni catalysts to generate nitrenes from aromatic azides. These Ni2 nitrenes are used towards selective C(sp2 )−H bond amination in order to generate indole and carbazole derivatives. This work highlights the unique properties of the Ni2imide that enable a 1,2-addition pathway, which contrasts known bimetallic nitrene insertion reactions. A detailed mechanistic study, primarily using density functional theory (DFT) is the focus of this chapter.Chapter two of this dissertation focuses on nitrene group transfer. In particular, this chapter highlights the ability of the dinuclear Ni catalyst [i-PrNDI]Ni2(C6H6) to react with aromatic azides to perform N=N coupling. A large scope of functional groups are tolerated in high yield with short reaction times. Catalyst comparison studies, studies on relevant catalytic intermediates for N=N coupling and reaction kinetics are shown in this chapter. Lastly, chapter three showcases the expansion of the nitrene group transfer ability of [ i-PrNDI]Ni2(C6H6) to generate high molecular weight azopolymers from aromatic diazides. These azopolymers are generated from monomers often used in organic semi-conducting materials. End group control and post polymer functionalization are highlighted in this chapter. Lastly, this work showcases a new polymer, polyazoisoindigo, as the first organic semiconducting material that reversibly transitions from a colored to colorless state upon reduction.
- Subject Added Entry-Topical Term
- Hydrocarbons.
- Subject Added Entry-Topical Term
- Oxidation.
- Subject Added Entry-Topical Term
- Cytochrome.
- Subject Added Entry-Topical Term
- Carbon.
- Subject Added Entry-Topical Term
- Polymerization.
- Subject Added Entry-Topical Term
- Hydrogen.
- Subject Added Entry-Topical Term
- Decomposition.
- Subject Added Entry-Topical Term
- Kinetics.
- Subject Added Entry-Topical Term
- Catalysis.
- Subject Added Entry-Topical Term
- Enzymes.
- Subject Added Entry-Topical Term
- Nitrogen.
- Subject Added Entry-Topical Term
- Competition.
- Subject Added Entry-Topical Term
- Inorganic chemistry.
- Subject Added Entry-Topical Term
- Molecular chemistry.
- Subject Added Entry-Topical Term
- Organic chemistry.
- 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:643118
MARC
008240221s2021 ulk 00 kor■001000016932639
■00520240214100525
■006m o d
■007cr#unu||||||||
■020 ▼a9798379832261
■035 ▼a(MiAaPQ)AAI30504903
■035 ▼a(MiAaPQ)Purdue15044229
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a551.5
■1001 ▼aAndjaba, John M.
■24510▼aCatalytic Nitrene Reactions Enabled by Dinuclear Nickel Catalysts▼h[electronic resource]
■260 ▼a[S.l.]▼bPurdue University. ▼c2021
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2021
■300 ▼a1 online resource(513 p.)
■500 ▼aSource: Dissertations Abstracts International, Volume: 85-01, Section: B.
■500 ▼aAdvisor: Uyeda, Christopher.
■5021 ▼aThesis (Ph.D.)--Purdue University, 2021.
■506 ▼aThis item must not be sold to any third party vendors.
■520 ▼aNitrenes are reactive intermediates that are known to generate high interest organic molecules. Due to their inherent instability, nitrenes are often stabilized by introducing them to transition metal complexes. Many transition metal stabilized nitrenes (M=NR2) have been reported and some of these complexes have been shown to control nitrene reactivity and selectivity. Transition metal nitrene reactivity can be categorized into two main groups: bond-insertion and group transfer reactions. In the reference to the former, chapter one of this dissertation highlights using unique dinuclear Ni catalysts to generate nitrenes from aromatic azides. These Ni2 nitrenes are used towards selective C(sp2 )−H bond amination in order to generate indole and carbazole derivatives. This work highlights the unique properties of the Ni2imide that enable a 1,2-addition pathway, which contrasts known bimetallic nitrene insertion reactions. A detailed mechanistic study, primarily using density functional theory (DFT) is the focus of this chapter.Chapter two of this dissertation focuses on nitrene group transfer. In particular, this chapter highlights the ability of the dinuclear Ni catalyst [i-PrNDI]Ni2(C6H6) to react with aromatic azides to perform N=N coupling. A large scope of functional groups are tolerated in high yield with short reaction times. Catalyst comparison studies, studies on relevant catalytic intermediates for N=N coupling and reaction kinetics are shown in this chapter. Lastly, chapter three showcases the expansion of the nitrene group transfer ability of [ i-PrNDI]Ni2(C6H6) to generate high molecular weight azopolymers from aromatic diazides. These azopolymers are generated from monomers often used in organic semi-conducting materials. End group control and post polymer functionalization are highlighted in this chapter. Lastly, this work showcases a new polymer, polyazoisoindigo, as the first organic semiconducting material that reversibly transitions from a colored to colorless state upon reduction.
■590 ▼aSchool code: 0183.
■650 4▼aHydrocarbons.
■650 4▼aOxidation.
■650 4▼aCytochrome.
■650 4▼aCarbon.
■650 4▼aPolymerization.
■650 4▼aHydrogen.
■650 4▼aDecomposition.
■650 4▼aKinetics.
■650 4▼aCatalysis.
■650 4▼aEnzymes.
■650 4▼aNitrogen.
■650 4▼aCompetition.
■650 4▼aInorganic chemistry.
■650 4▼aMolecular chemistry.
■650 4▼aOrganic chemistry.
■690 ▼a0490
■690 ▼a0488
■690 ▼a0431
■71020▼aPurdue University.
■7730 ▼tDissertations Abstracts International▼g85-01B.
■773 ▼tDissertation Abstract International
■790 ▼a0183
■791 ▼aPh.D.
■792 ▼a2021
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T16932639▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
■980 ▼a202402▼f2024
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