• Login
    View Item 
    •   Home
    • Office of Sponsored Research (OSR)
    • KAUST Funded Research
    • Publications Acknowledging KAUST Support
    • View Item
    •   Home
    • Office of Sponsored Research (OSR)
    • KAUST Funded Research
    • Publications Acknowledging KAUST Support
    • 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 LibguideTheses and Dissertations LibguideSubmit an Item

    Statistics

    Display statistics

    Synthesis of a Bis(thiophenolate)pyridine Ligand and Its Titanium, Zirconium, and Tantalum Complexes

    • CSV
    • RefMan
    • EndNote
    • BibTex
    • RefWorks
    Type
    Article
    Authors
    Lenton, Taylor N.
    VanderVelde, David G.
    Bercaw, John E.
    Date
    2012-10-18
    Online Publication Date
    2012-10-18
    Print Publication Date
    2012-11-12
    Permanent link to this record
    http://hdl.handle.net/10754/599834
    
    Metadata
    Show full item record
    Abstract
    A precursor to a new tridentate LX 2 type ligand, bis(thiophenol)pyridine ((SNS)H 2 = (2-C 6H 4SH) 2-2,6-C 5H 3N), was prepared. Bis(thiophenolate)pyridine complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex (SNS)Zr(NMe 2) 2 (4) displays C 2 symmetry in the solid state, unlike a related bis(phenolate)pyridine compound, C s-symmetric (ONO)Ti(NMe 2) 2. This change is likely the result of strain about the sulfur atom in the six-membered chelate with longer metal-sulfur and carbon-sulfur bonds. Solid-state structures of tantalum complexes (SNS)Ta(NMe 2) 3 (5) and (SNS)TaCl(NEt 2) 2 (6) also display pronounced C 2 twisting of the SNS ligand. 1D and 2D NMR experiments show that 5 is fluxional, with rotation about the Ta-N(amide) bonds occurring on the NMR time scale that interchange the equatorial amide methyl groups (ΔG ‡ 393 = 25.0(3) kcal/mol). The fluxional behavior of 6 in solution was also studied by variable-temperature 1H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR time scale in one diastereomeric conformation at temperatures below -50 °C, fast rotation about the equatorial amide Ta-N bonds occurs at higher temperature (ΔG ‡ 393 = 13.4(3) kcal/mol), and exchange of diastereomeric methylene protons occurs via inversion at Ta that interconverts antipodes (ΔG ‡ 393 ≈ 14(1) kcal/mol). © 2012 American Chemical Society.
    Citation
    Lenton TN, VanderVelde DG, Bercaw JE (2012) Synthesis of a Bis(thiophenolate)pyridine Ligand and Its Titanium, Zirconium, and Tantalum Complexes. Organometallics 31: 7492–7499. Available: http://dx.doi.org/10.1021/om300789h.
    Sponsors
    This work was supported by a KAUST Center-In-Development Grant to King Fahd University of Petroleum and Minerals (Dhahran, Saudi Arabia) and the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431). We thank Ian A. Tonks and Matthew S. Winston for helpful discussions related to the research present in this paper. We also thank Lawrence M. Henling and Michael W. Day of Caltech for solving crystal structures. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094).
    Publisher
    American Chemical Society (ACS)
    Journal
    Organometallics
    DOI
    10.1021/om300789h
    ae974a485f413a2113503eed53cd6c53
    10.1021/om300789h
    Scopus Count
    Collections
    Publications Acknowledging KAUST Support

    entitlement

     
    DSpace software copyright © 2002-2022  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.