• Login
    View Item 
    •   Home
    • Theses and Dissertations
    • Theses and Dissertations
    • View Item
    •   Home
    • Theses and Dissertations
    • Theses and Dissertations
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Browse

    All of TUScholarShareCommunitiesDateAuthorsTitlesSubjectsGenresThis CollectionDateAuthorsTitlesSubjectsGenres

    My Account

    LoginRegister

    Help

    AboutPeoplePoliciesHelp for DepositorsData DepositFAQs

    Statistics

    Most Popular ItemsStatistics by CountryMost Popular Authors

    Anion effects in Homogeneous Palladium and Gold Catalysis

    • CSV
    • RefMan
    • EndNote
    • BibTex
    • RefWorks
    Thumbnail
    Name:
    TETDEDXWozniak-temple-0225E-13 ...
    Size:
    19.86Mb
    Format:
    PDF
    Download
    Genre
    Thesis/Dissertation
    Date
    2019
    Author
    Wozniak, Derek Ian
    Advisor
    Dobereiner, Graham
    Committee member
    Zdilla, Michael J., 1978-
    Wengryniuk, Sarah E.
    Theopold, Klaus (Klaus Hellmut)
    Department
    Chemistry
    Subject
    Inorganic Chemistry
    Chemistry, Organic
    Anion
    Catalysis
    Coordination
    Gold
    Palladium
    Permanent link to this record
    http://hdl.handle.net/20.500.12613/4054
    
    Metadata
    Show full item record
    DOI
    http://dx.doi.org/10.34944/dspace/4036
    Abstract
    The overarching theme of this work is to use weak interactions to improve transition metal catalysis by studying the ways transition metal cations interact with both traditional and novel weakly-coordinating anions. Understanding of these interactions will better allow synthetic chemists to choose appropriate counterions for catalytic transformations, as well as giving mechanistic insight for organometallic reactivity. Additionally, new anions can be synthesized with specific functionalities to improve reactions of interest. A series of ion pairs featuring the [Pd(IPr)(C(O)C6H¬9N)]+ cation were synthesized with various weakly-coordinating anions. Solid- and solution-state interactions with the anions were investigated using X-ray crystallography, NMR and IR spectroscopy, and computation. Proton NMR and percent buried volume calculations inform on the steric properties of the anions, whereas IR and DFT report on the electronics of anion binding. A qualitative scale of anion coordinating ability was created. In the process of this study, a new anion [IMP-H] – was also synthesized based on a phenylimidazole core. A variety of these functionalized [IMP-R] – anions were synthesized, with functionalities such as electron withdrawing groups, tertiary amides, and benzylic alcohols and amines. The coordinating abilities of these anions were analyzed with the techniques described above, with fairly large differences observed between the various functionalities. Further functionalization of these anions may be beneficial from a catalytic standpoint, as coordinating ability of anions has been shown to have dramatic effects on catalytic activity. By designing particular functionalities on anions, efficiency of catalytic processes may be markedly improved. To investigate the effects of the functionalized anions on catalysis, the anions were paired with gold cations such as [(IPr)Au(NCMe)]+, [(JohnPhos)Au(NCMe)]+, and [(tBuXPhos)Au(NCMe)]+. These ion pairs were used as catalysts for several reactions known to show differences in reactivity based on the anion present. While the IPr- and JohnPhos-containing ion pairs both resulted in the formation of gold nanoparticles under various reaction conditions, the tBuXPhos complexes did not, and were therefore more amenable to study. Mild anion effects were seen in the gold-catalyzed hydroalkoxylation of 3-hexyne as well as gold-catalyzed intermolecular [2+2] cycloaddition of α-methylstyrene and phenylacetylene; solvent polarity was also found to have a major effect on the reaction. Other reactions investigated include alkyne hydration, isomerization of 5-hexyn-1-ol to form cyclic vinyl ethers, and propargylation of substituted benzaldehydes.
    ADA compliance
    For Americans with Disabilities Act (ADA) accommodation, including help with reading this content, please contact scholarshare@temple.edu
    Collections
    Theses and Dissertations

    entitlement

     
    DSpace software (copyright © 2002 - 2023)  DuraSpace
    Temple University Libraries | 1900 N. 13th Street | Philadelphia, PA 19122
    (215) 204-8212 | scholarshare@temple.edu
    Open Repository is a service operated by 
    Atmire NV
     

    Export search results

    The export option will allow you to export the current search results of the entered query to a file. Different formats are available for download. To export the items, click on the button corresponding with the preferred download format.

    By default, clicking on the export buttons will result in a download of the allowed maximum amount of items.

    To select a subset of the search results, click "Selective Export" button and make a selection of the items you want to export. The amount of items that can be exported at once is similarly restricted as the full export.

    After making a selection, click one of the export format buttons. The amount of items that will be exported is indicated in the bubble next to export format.