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

    Browse

    All of KAUSTCommunitiesIssue DateSubmit DateThis CollectionIssue DateSubmit Date

    My Account

    Login

    Quick Links

    Open Access PolicyORCID LibguidePlumX LibguideSubmit an Item

    Statistics

    Display statistics

    Metathesis of functionalized alkanes: understanding the unsolved problem

    • CSV
    • RefMan
    • EndNote
    • BibTex
    • RefWorks
    Thumbnail
    Name:
    Dissertation Mykyta (1).pdf
    Size:
    9.496Mb
    Format:
    PDF
    Description:
    Mykyta Tretiakov - Final Paper
    Download
    View more filesView fewer files
    Type
    Dissertation
    Authors
    Tretiakov, Mykyta cc
    Advisors
    Basset, Jean-Marie cc
    Committee members
    Huang, Kuo-Wei cc
    Bakr, Osman cc
    Saikaly, Pascal cc
    Program
    Chemical Science
    KAUST Department
    Physical Science and Engineering (PSE) Division
    Date
    2019-10
    Permanent link to this record
    http://hdl.handle.net/10754/659546
    
    Metadata
    Show full item record
    Abstract
    The aim of this dissertation is to discover the metathesis of functionalized alkane. The first chapter describes an overview of the catalysis field, the role of surface organometallic chemistry (SOMC) and the history of metathesis. The second chapterstudies the decomposition of the alkane metathesis catalyst precursor based on WMe6 grafted on partially dehydroxylated at 700 °C silica (SiO2-700) [≡Si-O-WMe5] and its activity in the metathesis of non-coordinating substrates. We used thermal programmed desorption (TPD), in situ infrared-mass spectrometry (IRMS) and chemical techniques with nuclear magnetic resonance. We found evidence of decomposition of the catalyst by coordinating substrates (ester and alcohol) and its inactivity in the metathesis of siloxanes and silanes. [≡Si-O-WMe5] catalyzes the disproportionation of n-butyl-ferrocene to ferrocene and dibutylferrocene. The third chapter is dedicated to the strategy of protection of the catalyst active site by modification of the catalyst support. We modified conventional silica which was partially dehydroxylated at 500 °C, and KCC-1 supports by octyltriethoxysilane as well as 1,1,2,2- tetrahydro-perfluorooctyl-triethoxysilane and grafted the alkane metathesis catalyst precursor – W(CH3)6. The obtained materials have been thoroughly characterized and studied in catalysis showing the activity towards metathesis of olefins and alkanes, but were inactive in the metathesis of functionalized alkanes. The fourth chapter provides the strategy with which to design and metathesize a compatible functionalized alkane on well-defined alkane metathesis catalyst. We investigated the weak coordinating pyrrole-based family of substrates. While utilizing [≡Si-O-WMe5] with 1-(alkyl)-2,5-dimethyl-1H-pyrroles, traces of metathesis and isomerization products were observed. With these results, we synthesized a rigid aromatic molecule – 9-hexyl-9H-carbazole and reached 5 % conversion to lower and higher homologs. That result proved to be the first-ever known example of metathesis of a functionalized alkane.
    Citation
    Tretiakov, M. (2019). Metathesis of functionalized alkanes: understanding the unsolved problem. KAUST Research Repository. https://doi.org/10.25781/KAUST-4G3C1
    DOI
    10.25781/KAUST-4G3C1
    ae974a485f413a2113503eed53cd6c53
    10.25781/KAUST-4G3C1
    Scopus Count
    Collections
    Dissertations; Physical Science and Engineering (PSE) Division; Chemical Science Program

    entitlement

     
    DSpace software copyright © 2002-2021  DuraSpace
    Quick Guide | Contact Us | KAUST University Library
    Open Repository is a service hosted 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. For anonymous users the allowed maximum amount is 50 search results.

    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.