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Iridium catalyzed alkane dehydrogenation, olefin isomerization and related chemistry

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TitleInfo (displayLabel = Citation Title); (type = uniform)
Title
Iridium catalyzed alkane dehydrogenation, olefin isomerization and related chemistry
Name (ID = NAME001); (type = personal)
NamePart (type = family)
Ray
NamePart (type = given)
Amlan
DisplayForm
Amlan Ray
Role
RoleTerm (authority = RULIB)
author
Name (ID = NAME002); (type = personal)
NamePart (type = family)
Goldman
NamePart (type = given)
Alan
Affiliation
Advisory Committee
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Alan S. Goldman
Role
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chair
Name (ID = NAME003); (type = personal)
NamePart (type = family)
Krogh-Jespersen
NamePart (type = given)
Karsten
Affiliation
Advisory Committee
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Karsten Krogh-Jespersen
Role
RoleTerm (authority = RULIB)
internal member
Name (ID = NAME004); (type = personal)
NamePart (type = family)
Uhrich
NamePart (type = given)
Kathryn
Affiliation
Advisory Committee
DisplayForm
Kathryn E. Uhrich
Role
RoleTerm (authority = RULIB)
internal member
Name (ID = NAME005); (type = personal)
NamePart (type = family)
Sheridan
NamePart (type = given)
John
Affiliation
Advisory Committee
DisplayForm
John B. Sheridan
Role
RoleTerm (authority = RULIB)
outside member
Name (ID = NAME006); (type = corporate)
NamePart
Rutgers University
Role
RoleTerm (authority = RULIB)
degree grantor
Name (ID = NAME007); (type = corporate)
NamePart
Graduate School - New Brunswick
Role
RoleTerm (authority = RULIB)
school
TypeOfResource
Text
Genre (authority = marcgt)
theses
OriginInfo
DateCreated (qualifier = exact)
2007
DateOther (qualifier = exact); (type = degree)
2007
Language
LanguageTerm
English
PhysicalDescription
Form (authority = marcform)
electronic
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application/pdf
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text/xml
Extent
xxii, 164 pages
Abstract
Excellent alkane dehydrogenation activity exhibited by the pincer-ligated iridium complexes of the type -- (X-RPCP)IrH2 (X-RPCP = 4-X-C6H2-2,6-(CH2PR2)2 with X = H, MeO; R = tBu, iPr) was exploited to functionalize a variety of aliphatic polyolefins via catalytic dehydrogenation. Of the two (MeO-RPCP)IrH2 complexes (2 : R = tBu and 3 : R = iPr) used for the study, 3 was found to be an extremely active system for dehydrogenation of poly(1-hexene), giving 100% conversion with respect to the initial concentration of norbornene (acceptor) used. The catalysts exhibited selectivity for dehydrogenation of polymer branches over the backbone, with a kinetic selectivity for terminal position of the branches.
Isomerization of 1-octene conducted with iridium-pincer complexes 1 ((H-tBuPCP)IrH2) 2 and 3, having different steric and electronic tuning, suggested that a larger alkyl group (R) on the phosphines along with a stronger [pi sign]-donating group on the pincer aryl ring (X) resulted in lower rate and higher selectivity for isomerization. In a related study, insertion of an olefin into the Ir-H bonds of the complexes (H-tBuPCP)Ir(H)(Y) were investigated using cis-1,2-dideutero-1-octene as the substrate. In presence of the substrate octene, some (H-tBuPCP)Ir(H)(Y) complexes (Y = Ph, NHPh etc) showed labile behavior in solution, being present in equilibrium with a (H-tBuPCP)Ir(H)(1-octene) complex. Results of kinetic experiments suggested that [pi sign]-donating Y groups enhanced the rate of olefin insertion. DFT calculations carried out on the systems predicted a slight preference for a pathway in which olefin binds to the metal center in between H and Y with a trans arrangement to the PCP-aryl ring. The olefin bound 14-electron complex (PCP)Ir(1-octene) was characterized by low temperature 1H and 31P NMR.
A new pincer complex (Me2N-tBuPCP)IrH2 (4d), having [pi sign]-electron rich iridium center, was synthesized and investigated for catalytic dehydrogenation. Complex 4d, was found to exhibit better selectivity and rate, as compared to the previously reported systems 1 and 2, for transfer dehydrogenation of branched and n-alkanes. It was also found to be a robust, slightly more stable and highly efficient catalyst for acceptorless dehydrogenation of cyclodecane.
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references.
Subject (ID = SUBJ1); (authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject (ID = SUBJ2); (authority = ETD-LCSH)
Topic
Alkanes
Subject (ID = SUBJ3); (authority = ETD-LCSH)
Topic
Iridium catalysts
Subject (ID = SUBJ4); (authority = ETD-LCSH)
Topic
Dehydrogenation
Subject (ID = SUBJ5); (authority = ETD-LCSH)
Topic
Alkenes
Subject (ID = SUBJ6); (authority = ETD-LCSH)
Topic
Isomerization
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Identifier (type = hdl)
http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.16759
Identifier
ETD_409
Location
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NjNbRU
Identifier (type = doi)
doi:10.7282/T3ZW1M9M
Genre (authority = ExL-Esploro)
ETD doctoral
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The author owns the copyright to this work.
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Name
Amlan Ray
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Copyright holder
Affiliation
Rutgers University. Graduate School - New Brunswick
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Non-exclusive ETD license
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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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