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Mass spectrometric and computational studies of N-heterocycles

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Title
Mass spectrometric and computational studies of N-heterocycles
Name (type = personal)
NamePart (type = family)
Wang
NamePart (type = given)
Ning
NamePart (type = date)
1987-
DisplayForm
Ning Wang
Role
RoleTerm (authority = RULIB)
author
Name (type = personal)
NamePart (type = family)
Lee
NamePart (type = given)
Jeehiun
DisplayForm
Jeehiun Lee
Affiliation
Advisory Committee
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chair
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NamePart (type = family)
Romsted
NamePart (type = given)
Laurence
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Laurence Romsted
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Advisory Committee
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RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Warmuth
NamePart (type = given)
Ralf
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Ralf Warmuth
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Chen
NamePart (type = given)
Mu
DisplayForm
Mu Chen
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
outside member
Name (type = corporate)
NamePart
Rutgers University
Role
RoleTerm (authority = RULIB)
degree grantor
Name (type = corporate)
NamePart
School of Graduate Studies
Role
RoleTerm (authority = RULIB)
school
TypeOfResource
Text
Genre (authority = marcgt)
theses
OriginInfo
DateCreated (encoding = w3cdtf); (keyDate = yes); (qualifier = exact)
2019
DateOther (encoding = w3cdtf); (qualifier = exact); (type = degree)
2019-10
Language
LanguageTerm (authority = ISO 639-3:2007); (type = text)
English
Abstract (type = abstract)
This dissertation focuses on the experimental and theoretical studies of thermodynamic properties and reactivity of two types of heterocyclic compounds: N-heterocyclic carbenes (NHCs) and imidazoles.

In recent years, triazolylidene carbenes have drawn broad attention in stereoselective organo-catalysis. These carbenes have dominated over thiazolylidene and imidazolylidene carbenes with drastic improvement in the achievable stereoselectivity in a variety of NHC-catalyzed reactions. Although intensively applied and studied in a great variety of catalytic transformations, the intrinsic properties of these carbenes remain mostly unknown. Our group therefore measured and calculated the gas phase acidities of a series triazolium pre-catalysts (the conjugate acids of triazolylidene carbenes), both achiral and chiral, with mass spectrometric experiments and quantum mechanical methods to probe their fundamental properties. It was found that the gas phase acidities of the triazolium pre-catalysts can be tuned by the subtle electronic properties of their substituents on the triazolium ring. The correlation between the thermodynamic properties and the catalytic reactivities has also been discovered and further investigated. We have found the correlations between the gas phase acidities of these triazolium pre-catalysts and the stereoselectivity of two triazolylidene carbene-catalyzed Umpolung reactions. These correlations, the first of their kind, can be potentially used to provide guidance for future stereoselective catalyst design. These results are discussed in Chapter 2.

Carbon dioxide capture and sequestration (CCS) has become a research “hotspot” due to the increasing concern regarding their roles in the global greenhouse effect and subsequent climate change and environment destruction. We investigated the role that imidazolate anion plays in the absorption of carbon dioxide. A series of imidazoles with structural variations were characterized with both mass spectrometric experiments and computer modeling, in the gas phase and in an ionic liquid medium. By establishing correlations between the imidazolate properties and CO2 absorption capacity, we hope to provide guidance for a future generation of greenhouse gas capture systems with improved efficiency and robustness. During this process, we have also analyzed the substitution effects on the imidazolate properties and CO2 capture, and confirmed that mass spectrometry-based experiments can be designed to investigate tautomerism of imidazoles. These results are discussed in Chapter 3.

The difference in reactivity of organic species in solution phase compared to gas phase has interested many organic chemists. Gas phase studies using mass spectrometry allow us to penetrate the intrinsic property of various organic species and elucidate reaction mechanisms without solvent effects. Only charged species could be detected by mass spectroscopy, and organocatalysts with charged handles are therefore important for such purposes. In Chapter 4, we discussed how we could utilize the charge-handled NHCs in Umpolung reactions such as Stetter reaction and benzoin condensation in the gas phase. Selected imidazolylidene, thiazolylidene and triazolylidene carbenes, either synthesized ab initio or commercially available, were examined both experimentally and theoretically.

Finally, in Chapter 5, we reported the preliminary data collected that explore the relationship between the gas-phase properties of ionic liquids (cations/anions) with proton conductivity/open-circuit potential (OCP) of ionic liquid-based electrolytes used in anhydrous fuel cells.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject (authority = LCSH)
Topic
Heterocyclic compounds -- Thermomechanical properties
Subject (authority = LCSH)
Topic
Mass spectrometry
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_10330
PhysicalDescription
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application/pdf
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text/xml
Extent
1 online resource (xvi, 119 pages) : illustrations
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
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Title
School of Graduate Studies Electronic Theses and Dissertations
Identifier (type = local)
rucore10001600001
Location
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NjNbRU
Identifier (type = doi)
doi:10.7282/t3-da56-5z79
Genre (authority = ExL-Esploro)
ETD doctoral
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The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Wang
GivenName
Ning
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2019-09-25 15:43:29
AssociatedEntity
Name
Ning Wang
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Copyright holder
Affiliation
Rutgers University. School of Graduate Studies
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I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
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Copyright protected
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Open
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DateCreated (point = end); (encoding = w3cdtf); (qualifier = exact)
2019-11-12T17:00:36
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