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Synthesis of amine-functionalized bis(imidazolium)borate salts: novel bis(carbene)borate ligand precursors
Descriptive
TitleInfo
Title
Synthesis of amine-functionalized bis(imidazolium)borate salts: novel bis(carbene)borate ligand precursors
Name
(type = personal)
NamePart
(type = family)
Karagiannis
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Ageliki
NamePart
(type = date)
1990
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Karagiannis, Ageliki, 1990-
Role
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author
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(type = family)
Jaekle
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(type = given)
Frieder
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Frieder Jaekle
Affiliation
Advisory Committee
Role
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(authority = RULIB)
chair
Name
(type = personal)
NamePart
(type = family)
Prokopchuk
NamePart
(type = given)
Demyan
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Demyan Prokopchuk
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Advisory Committee
Role
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(authority = RULIB)
internal member
Name
(type = personal)
NamePart
(type = family)
Lockard
NamePart
(type = given)
Jenny
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Jenny Lockard
Affiliation
Advisory Committee
Role
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(authority = RULIB)
internal member
Name
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NamePart
Rutgers University
Role
RoleTerm
(authority = RULIB)
degree grantor
Name
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NamePart
Graduate School - Newark
Role
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school
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Text
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theses
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2020
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2020-05
Language
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English
Abstract
(type = abstract)
N-heterocyclic carbenes (NHCs), commonly derived from N,N’-disubstituted imidazolium salts, have gained popularity since their isolation by Arduengo in 1991 and their application as ligands for catalysis by Herrmann in the mid-1990s. An underexplored area of research is the examination of chelating ligands incorporating amine-functionalized bis(NHC) ligands. This thesis focuses on the synthesis of novel bis(imidazolium) borate salts and the preliminary formation of their NHCs. Early attempts of reacting imidazoles with chlorobis(amino)borane reagents yielded incomplete reactions or decomposition, which are likely the consequence of a steric and/or electronic mismatch between boron and its attached amines. After testing several chloroaminoborane reagents, two novel amine-functionalized bis(imidazolium)borate salts have been successfully synthesized and characterized. By reacting 1-tert-butylimidazole (tBuIm) or 1-methylimidazole (MeIm) with iPr2N(Ph)BCl at room temperature, the salts [iPr2NB(Ph)(tBuIm)2][OTf] and [iPr2NB(Ph)(MeIm)2][OTf] (OTf = trifluroomethanesulfonate) can be prepared using a two-step, one-pot synthetic protocol. Halide abstraction using AgOTf to form the proposed intermediate iPr2NB(Ph)OTf, followed by imidazole addition readily produces the target imidazolium borate salts. Optimization efforts resulted in the discovery of a solvent-dependent mechanism in CH3CN versus CH2Cl2 during addition of AgOTf to iPr2NB(Ph)Cl. In both solvents, the desired product is obtained, however the coordinating effects of CH3CN may play a role in minimizing undesirable product formation. Overall, a reliable synthetic method to obtain amine-functionalized bis(imidazolium)borate salts is presented. Preliminary data suggests that deprotonation leads to carbene formation, however more experiments are needed to fully characterize the product. This work holds promise to prepare novel bis(carbene)aminoborates as proton-responsive ligands for electrocatalytic H2 oxidation/production.
Subject
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Topic
Bis(imidazolium)borate salts
Subject
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Topic
Chemistry
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TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier
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ETD
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TitleInfo
Title
Graduate School - Newark Electronic Theses and Dissertations
Identifier
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rucore10002600001
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ETD_10857
Identifier
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doi:10.7282/t3-epev-0c12
PhysicalDescription
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application/pdf
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text/xml
Extent
1 online resource (viii, 44 pages)
Note
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M.S.
Note
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Includes bibliographical references
Location
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NjNbRU
Genre
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ETD graduate
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Rights
RightsDeclaration
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The author owns the copyright to this work.
RightsHolder
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Name
FamilyName
Karagiannis
GivenName
Ageliki
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime
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(qualifier = exact);
(point = start)
2020-04-28 01:10:05
AssociatedEntity
Name
Ageliki Karagiannis
Role
Copyright holder
Affiliation
Rutgers University. Graduate School - Newark
AssociatedObject
Type
License
Name
Author Agreement License
Detail
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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Embargo
DateTime
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2020-05-31
DateTime
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2022-05-31
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after May 31st, 2022.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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windows xp
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2020-05-02T18:08:44
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2020-05-02T18:08:44
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