THE DEVELOPMENT AND APPLICATION OF TRANSITION METAL–HYRDIDES IN CATALYSIS FOR ALKENE HYDROSILYLATION AND ISOMERIATION REACTIONS

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dc.contributor.advisorCook, Amanda
dc.contributor.authorChang, Alison
dc.date.accessioned2024-08-07T19:47:59Z
dc.date.available2024-08-07T19:47:59Z
dc.date.issued2024-08-07
dc.description.abstractMetal-mediated alkene transformations is a rapidly developing field to obtain various organic precursors for pharmaceutical compounds, industrial chemicals, and consumer products. The pursuit of developing Earth-abundant catalysts is of great interest due to catalyst affordability in comparison to precious metal catalysts. Specifically, Ni catalysts serve as viable alternatives to previous metal catalysts due to the versatile reactivity of Ni. In addition to catalyst development, the catalyst mechanism is also just as important to inform future catalyst design. This often results in guided catalyst optimization and byproduct inhibition. The focal point of this thesis surrounds the development and investigation of Ni-catalyzed alkene hydrosilylation and alkene isomerization. Particularly, the formation of Ni–H intermediates to mediate these organic transformations. Reaction and catalyst optimization, substrate scope, and mechanism determination are reported for both alkene hydrosilylation and isomerization systems. Chapter I highlights the utility of Ni–H in these organic reactions, motivating our work described in Chapters II-VI. Chapter II reports on the reaction development and substrate scope of the homogeneous hydrosilylation (NHC)Ni (NHC = N-heterocyclic carbene) catalyst. Chapter III outlines the mechanistic investigation of the (NHC)Ni-catalyzed alkene hydrosilylation system described in Chapters II. Chapter IV is a continuation of the catalytic system developed in Chapter II and III and delves more deeply to explore the electronic structure of (NHC)Ni(alkene) catalysts. Modification of the NHC ligand gives rise to trends in catalytic ability. To obtain a deeper understanding of this system, ligand steric and electronic variation are tested to observe its influence on catalyst behavior. Chapter V illustrates the incorporation of the in situ hydrosilylation system developed in Chapter II into the remote hydrosilylation of a long chain alkene. This work also includes preliminary data on an in situ generated Ni-catalyzed alkene isomerization system in combination with a hydrosilylation system to install a silicon group distal to the initial reaction site. Chapter VI outlines the development, characterization, and investigation of a heterogeneous Ni alkene isomerization system. This chapter includes catalyst substrate scope, preliminary mechanistic data, and comparison to other Ni-catalyzed alkene isomerization systems. This dissertation includes previously published and unpublished coauthored material.en_US
dc.identifier.urihttps://hdl.handle.net/1794/29687
dc.language.isoen_US
dc.publisherUniversity of Oregon
dc.rightsAll Rights Reserved.
dc.subjectcatalysisen_US
dc.subjectcatalysten_US
dc.subjectheterogeneous catalysisen_US
dc.subjecthomogeneous catalysisen_US
dc.subjectorganometallicsen_US
dc.subjectreaction mechanismen_US
dc.titleTHE DEVELOPMENT AND APPLICATION OF TRANSITION METAL–HYRDIDES IN CATALYSIS FOR ALKENE HYDROSILYLATION AND ISOMERIATION REACTIONS
dc.typeElectronic Thesis or Dissertation
thesis.degree.disciplineDepartment of Chemistry and Biochemistry
thesis.degree.grantorUniversity of Oregon
thesis.degree.leveldoctoral
thesis.degree.namePh.D.

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