KUKU

KU ScholarWorks

  • myKU
  • Email
  • Enroll & Pay
  • KU Directory
    • Login
    View Item 
    •   KU ScholarWorks
    • Chemistry
    • Chemistry Scholarly Works
    • View Item
    •   KU ScholarWorks
    • Chemistry
    • Chemistry Scholarly Works
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Preparation, Characterization, and Electrochemical Activation of a Model [Cp*Rh] Hydride

    Thumbnail
    View/Open
    Boyd_2018.pdf (1.051Mb)
    Issue Date
    2018-09-26
    Author
    Boyd, Emily A.
    Lionetti, Davide
    Henke, Wade C.
    Day, Victor W.
    Blakemore, James D.
    Publisher
    American Chemical Society
    Type
    Article
    Article Version
    Scholarly/refereed, author accepted manuscript
    Rights
    Copyright © 2018 American Chemical Society
    Metadata
    Show full item record
    Abstract
    Monomeric half-sandwich rhodium hydride complexes are often proposed as intermediates in catalytic cycles, but relatively few such compounds have been isolated and studied, limiting understanding of their properties. Here, we report preparation and isolation of a monomeric rhodium(III) hydride complex bearing the pentamethylcyclopentadienyl (Cp*) and bis(diphenylphosphino)benzene (dppb) ligands. The hydride complex is formed rapidly upon addition of weak acid to a reduced precursor complex, Cp*Rh(dppb). Single-crystal X-ray diffraction data for the [Cp*Rh] hydride, which were previously unavailable for this class of compounds, provide evidence of the direct Rh–H interaction. Complementary infrared spectra show the Rh–H stretching frequency at 1986 cm−1. In contrast to results with other [Cp*Rh] complexes bearing diimine ligands, treatment of the isolated hydride with strong acid does not result in H2 evolution. Electrochemical studies reveal that the hydride complex can be reduced only at very negative potentials (ca. −2.5 V vs. ferrocenium/ferrocene), resulting in Rh–H bond cleavage and H2 generation. These results are discussed in the context of catalytic H2 generation, and development of design rules for improved catalysts bearing the [Cp*] ligand.
    Description
    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.8b02160.
    URI
    http://hdl.handle.net/1808/30787
    DOI
    https://doi.org/10.1021/acs.inorgchem.8b02160
    Collections
    • Chemistry Scholarly Works [553]
    Citation
    Boyd, E. A., Lionetti, D., Henke, W. C., Day, V. W., & Blakemore, J. D. (2019). Preparation, Characterization, and Electrochemical Activation of a Model [Cp*Rh] Hydride. Inorganic chemistry, 58(6), 3606–3615. https://doi.org/10.1021/acs.inorgchem.8b02160

    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