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Functionalization of alkanes and other hydrocarbons by high-oxidation state iridium
Descriptive
TitleInfo
Title
Functionalization of alkanes and other hydrocarbons by high-oxidation state iridium
SubTitle
catalyst design and mechanistic study
Name
(type = personal)
NamePart
(type = family)
Gao
NamePart
(type = given)
Yang
NamePart
(type = date)
1991-
DisplayForm
Yang Gao
Role
RoleTerm
(authority = RULIB)
author
Name
(type = personal)
NamePart
(type = family)
Goldman
NamePart
(type = given)
Alan S.
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Alan S. Goldman
Affiliation
Advisory Committee
Role
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chair
Name
(type = personal)
NamePart
(type = family)
Lipke
NamePart
(type = given)
Mark C.
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Mark C. Lipke
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
internal member
Name
(type = personal)
NamePart
(type = family)
Celik
NamePart
(type = given)
Fuat E.
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Fuat E. Celik
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
internal member
Name
(type = personal)
NamePart
(type = family)
Sheridan
NamePart
(type = given)
John
DisplayForm
John Sheridan
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
outside member
Name
(type = corporate)
NamePart
Rutgers University
Role
RoleTerm
(authority = RULIB)
degree grantor
Name
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NamePart
School of Graduate Studies
Role
RoleTerm
(authority = RULIB)
school
TypeOfResource
Text
Genre
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theses
OriginInfo
DateCreated
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2018
DateOther
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(type = degree)
2018-05
CopyrightDate
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2018
Place
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(type = code)
xx
Language
LanguageTerm
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(type = code)
eng
Abstract
(type = abstract)
The selective dehydrogenation of alkane and alkyl groups has a great impact on the synthesis of fuels and both commodity and fine chemicals. In this thesis, the work described is aimed at developing and understanding alkane functionalization using high-oxidation state Ir complexes. Simple Lewis acid such as Na+, Li+ or BAr3 were discovered to catalyze two of the most relevant and fundamental organometallic reactions with an Ir(III) species, (Phebox)Ir(OAc)(H) (Phebox = 2,6-bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl): olefin insertion and C‒H addition (and their respective microscopic reverse reactions). The results of DFT calculations indicate that the Lewis acid primarily promotes the opening of a vacant coordination site via interaction with acetate ligand. An acceptorless n-alkane dehydrogenation system was developed co-catalyzed by (Phebox)Ir(OAc)(H) and NaBArF4. Attempts to catalyze transfer dehydrogenation with (Phebox)Ir(OAc)(H)/Na+ afforded unexpected results. Alkane solutions of (Phebox)Ir(OAc)(H)/Na+ with 1-alkene added as hydrogen acceptor, in contrast with PCP-type catalysts, selectively effected transfer dehydrogenation of the olefins, olefin disproportionation to give mostly dienes. When ethylene was added as a hydrogen acceptor, we obtained high yields of dienes and polyenes, derived from ethylene oligomerization and dehydrogenation. These results indicate that Na+ catalyzed both insertion of olefins into the Ir-alkyl bond of (Phebox)Ir(OAc)(Alkyl), as well as C‒H activation by the same species. (Phebox)Ir(OAc)(H)/Na+ system was also discovered to catalyze the norbornene isomerization to form nortricyclane. An Ir(I) complex, (Phebox)Ir(η2-C2H4)2, was synthesized and discovered to catalyze the ethylene dehydrogenative coupling reaction via an iridacyclopentane intermediate. DFT calculation suggest that the iridacyclopentane intermediate undergoes a very unusual β-hydride elimination to give 1,3-butadiene.
Subject
(authority = RUETD)
Topic
Chemistry and Chemical Biology
RelatedItem
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TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier
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ETD
Identifier
ETD_8699
PhysicalDescription
Form
(authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
1 online resource (xv, 126 p. : ill.)
Note
(type = degree)
Ph.D.
Note
(type = bibliography)
Includes bibliographical references
Subject
(authority = ETD-LCSH)
Topic
Iridium
Subject
(authority = ETD-LCSH)
Topic
Catalysts
Note
(type = statement of responsibility)
by Yang Gao
RelatedItem
(type = host)
TitleInfo
Title
School of Graduate Studies Electronic Theses and Dissertations
Identifier
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rucore10001600001
Location
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NjNbRU
Identifier
(type = doi)
doi:10.7282/T3VX0KZR
Genre
(authority = ExL-Esploro)
ETD doctoral
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Rights
RightsDeclaration
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The author owns the copyright to this work.
RightsHolder
(type = personal)
Name
FamilyName
Gao
GivenName
Yang
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime
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(qualifier = exact);
(point = start)
2018-03-12 16:42:52
AssociatedEntity
Name
Yang Gao
Role
Copyright holder
Affiliation
Rutgers University. School of Graduate Studies
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.
RightsEvent
DateTime
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(qualifier = exact);
(point = start)
2018-05-31
DateTime
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(qualifier = exact);
(point = end)
2018-11-30
Type
Embargo
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after November 30th, 2018.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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windows xp
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