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Regioselectivity in catalytic transfer dehydrogenation and mechanism of 1-Alkene isomerization
Descriptive
TypeOfResource
Text
TitleInfo
(ID = T-1)
Title
Regioselectivity in catalytic transfer dehydrogenation and mechanism of 1-Alkene isomerization
Identifier
ETD_2939
Identifier
(type = hdl)
http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000056205
Language
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eng
Genre
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theses
Subject
(ID = SBJ-1);
(authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject
(ID = SBJ-2);
(authority = ETD-LCSH)
Topic
Alkanes
Subject
(ID = SBJ-3);
(authority = ETD-LCSH)
Topic
Isomerization
Subject
(ID = SBJ-4);
(authority = ETD-LCSH)
Topic
Dehydrogenation
Abstract
(type = abstract)
Bisphosphine and bisphohinite ligated pincer iridium complexes of the type (tBuPCP)IrHn (tBuPCP = C6H3-2,6-(CH2PtBu2)2, n=2, 4) and (tBuPOCOP)Ir(L) (tBuPOCOP = C6H3-2,6-(OPtBu2)2, L = H2, C2H4) are recognized to be outstanding catalyst precursors for transfer dehydrogenation of alkane. Catalytic regioselective dehydrogenation of alkane has a vast prospect. The catalytic transfer dehydrogenation property of these two pincer-iridium catalysts have been exploited in a tandem process known as Alkane Metathesis (AM), a process with enormous potential to transform lower hydrocarbons to higher hydrocarbons suitable for transportation fuel. Our studies here determine the difference between (tBuPCP)IrHn vs. (tBuPOCOP)Ir(L) in catalytic dehydrogenation of n-alkane to give regioselective alkenes is quite considerable. Hence we propose that this difference largely affects AM in the tandem system to result a product distribution of different molecular selectivity. We have found enormous disparity between these two complexes in terms of reactivity in different catalytic transfer dehydrogenation system. Kinetic, mechanistic and DFT (DFT by Prof. K. K. J et al.) studies predict that the subtle difference recognized in sterics exert major differences in the catalytic dehydrogenation. The sterics indicated here are mostly controlled by the alkyl groups attached to two phosphorous atom and the linkage in the pincer arm [-CH2- in (tBuPCP)Ir or –O- in (tBuPOCOP)Ir]. Catalytic 1-alkene isomerization is also another important reaction to study in this context as it has been well recognized to happen in parallel with n-alkane transfer dehydrogenation. All our different mechanistic, kinetic and DFT (DFT by Prof. K. K. J et al.) studies strongly indicate that the operative mechanism of 1-alkene isomerization is not previously presumed hydride-insertion pathway, which is very common in metal-hydride system. Although iridium-hydride plays a major role in catalytic transfer dehydrogenation, evidences indicate π-allyic mechanism of 1-alkene isomerization to be operative in this case. In addition our studies have gone in details to look into the elementary steps for π-allyic pathway. Besides these studies the transfer dehydrogenation technique has been exploited to determine different thermodynamic parameters of cycloalkanes of different ring sizes. In addition we have also investigated the regioselectivity in dehydrogenation of branch alkanes.
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electronic resource
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xxxi, 143 p. : ill.
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Note
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Ph.D.
Note
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Includes bibliographical references
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Includes vita
Note
(type = statement of responsibility)
by Soumik Biswas
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Biswas
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Soumik
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1979-
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author
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Soumik Biswas
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Goldman
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Alan S.
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chair
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Advisory Committee
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Alan S. Goldman
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Krogh-Jespersen
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Karsten
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internal member
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Advisory Committee
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Karsten Krogh-Jespersen
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Brennan
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John
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John Brennan
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Carolyn
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Advisory Committee
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Supplee Carolyn
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Rutgers University
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degree grantor
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Graduate School - New Brunswick
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school
OriginInfo
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2010
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2010
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xx
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Rutgers University Electronic Theses and Dissertations
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ETD
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Graduate School - New Brunswick Electronic Theses and Dissertations
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rucore19991600001
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Identifier
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doi:10.7282/T3Z31ZD5
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ETD doctoral
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Rights
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The author owns the copyright to this work.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
RightsHolder
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Name
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Biswas
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Soumik
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Permission or license
DateTime
2010-09-29 09:33:26
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Soumik Biswas
Affiliation
Rutgers University. Graduate School - New Brunswick
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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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