KUKU

KU ScholarWorks

  • myKU
  • Email
  • Enroll & Pay
  • KU Directory
    • Login
    View Item 
    •   KU ScholarWorks
    • Undergraduate Research at KU
    • Undergraduate Research, including Senior Theses
    • View Item
    •   KU ScholarWorks
    • Undergraduate Research at KU
    • Undergraduate Research, including Senior Theses
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    The End of the Rhodium: Synthesis, Characterization, and Redox Chemistry of Manganese and Rhodium Complexes Supported by Unorthodox Diimine Ligands

    Thumbnail
    View/Open
    Available after 2024/05/31 (6.248Mb)
    Issue Date
    2022-05
    Author
    Stiel, Jonah P.
    Publisher
    Department of Chemistry, University of Kansas
    Type
    Thesis
    Degree Level
    B.S.
    Discipline
    Chemistry
    Rights
    Copyright © 2022 by Jonah Philip Stiel
    Metadata
    Show full item record
    Abstract
    Economical storage of the large quantities of energy that could be generated by intermittent renewable sources, such as solar and wind, remains one of the largest unmet technical challenges hindering the widespread adoption of such technologies. Storing renewable energy in chemical bonds by means of molecular electrocatalysis represents a promising potential solution to this pressing issue. The 2,2′-bipyridyl (bpy) moiety is ubiquitous among the current generation of fuel production molecular electrocatalysts, yet a fundamental understanding of the properties which make it exceptionally attractive for enabling redox catalysis is lacking. In this thesis, model systems supported by unconventional analogues of bpy were investigated in order to elucidate the influence of steric and electronic effects on catalyst candidates supported by bpy-type ligands. In Chapter 2, the synthesis and characterization of manganese and ruthenium complexes supported by 4,5-diazafluorene and 9,9′-dimethyl-4,5-diazafluorene are discussed. These ligands were found to enforce wider bite angles and act as weaker sigma-donors in the complexes than bpy in analogous species. In Chapter 3, our work focusing on half-sandwich rhodium complexes supported by non-symmetrically mono-substituted bpy ligands bearing either a chloro or nitro substituent is detailed. Non-symmetric mono-substitution of the bpy ligand system was found to be an effective strategy for engendering new redox behavior at the metal center. Furthermore, the redox properties of the complexes supported by the mono-substituted bpy ligands were found to be intermediate between those of the parent complex supported by bpy and the symmetrically di-substituted complex supported by 4,4′-dinitro-2,2′-bipyridyl. Taken together, the findings reported in this thesis highlight the power of seemingly subtle ligand modifications in facilitating new redox chemistry with transition metal complexes.
    Description
    Submitted to the Faculty of the Department of Chemistry in Partial Fulfillment of the Requirements for Departmental Honors in Chemistry
    URI
    http://hdl.handle.net/1808/32767
    Collections
    • Undergraduate Research, including Senior Theses [63]

    Items in KU ScholarWorks are protected by copyright, with all rights reserved, unless otherwise indicated.


    We want to hear from you! Please share your stories about how Open Access to this item benefits YOU.


    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

    Browse

    All of KU ScholarWorksCommunities & CollectionsThis Collection

    My Account

    LoginRegister

    Statistics

    View Usage Statistics

    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

    The University of Kansas
      Contact KU ScholarWorks
    Lawrence, KS | Maps
     
    • Academics
    • Admission
    • Alumni
    • Athletics
    • Campuses
    • Giving
    • Jobs

    The University of Kansas prohibits discrimination on the basis of race, color, ethnicity, religion, sex, national origin, age, ancestry, disability, status as a veteran, sexual orientation, marital status, parental status, gender identity, gender expression and genetic information in the University’s programs and activities. The following person has been designated to handle inquiries regarding the non-discrimination policies: Director of the Office of Institutional Opportunity and Access, IOA@ku.edu, 1246 W. Campus Road, Room 153A, Lawrence, KS, 66045, (785)864-6414, 711 TTY.

     Contact KU
    Lawrence, KS | Maps