Catalysis is a technology of vital importance, enabling the production of many goods which are essential to the modern lifestyle. As such, the continued development of catalysis is of great importance, helping to reduce the costs and environment harm associated with the modern economy. This thesis describes the study and design of pincer iridium complexes, a type of organometallic complex which can catalyze multiple reactions, including alkane dehydrogenation. If these catalysts are developed sufficiently, in the future they may have commercial applications for the production of fuels and commodity chemicals. The research described in this thesis focused upon catalytic activity and selectivity, two aspects of a catalytic performance, for study and improvement. Understanding the steric and electronic properties which determine activity and selectivity, from a mechanistic viewpoint, should allowed for the rational and effective design of new, higher-performing catalysts. First, the regioselectivity of dehydrogenation was examined through a combination of experimental and computational methods. The influence of each steric and electronic factor was both identified and quantified. Next, catalytic activity was investigated using a similar approach, showing that massive changes in activity (orders of magnitude) could be attributed to a single electronic factor. With these mechanistic insights in hand, the rational design of new catalysts was begun. Computational studies suggested that cationic catalysts would be several hundred fold more active than their neutral counterparts, and synthetic progress was made in that direction. Carefully considering the mechanism of dehydrogenation also allowed for process chemistry improvements which increased activity significantly. Lastly, the role of additives to dehydrogenation was also investigated, showing that certain Brønsted bases improved catalytic activity significantly.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject (authority = ETD-LCSH)
Topic
Dehydrogenation
Subject (authority = ETD-LCSH)
Topic
Alkanes
Subject (authority = ETD-LCSH)
Topic
Catalysts
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_6993
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
1 online resource (xxxi, 256 p. : ill.)
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Michael John Blessent
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
Rutgers University. Graduate School - New Brunswick
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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.