ACS Publications. Most Trusted. Most Cited. Most Read

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2017, 56, 4, 1956-1965
RETURN TO ISSUEPREVArticleNEXT

[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ2-Ureato Compounds

View Author Information
H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47906, United States
*E-mail: [email protected]
Cite this: Inorg. Chem. 2017, 56, 4, 1956–1965
Publication Date (Web):February 6, 2017
https://doi.org/10.1021/acs.inorgchem.6b02547
Copyright © 2017 American Chemical Society
Request reuse permissions

    Article Views

    879

    Altmetric

    -

    Citations

    23
    LEARN ABOUT THESE METRICS
    Read OnlinePDF (2 MB)
    Get e-Alerts
    Supporting Info (8)»
    SUBJECTS:

    Abstract

    Abstract Image

    A new family of uranium(IV) imido complexes of the form Tp*2U(NR) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate; R = benzyl (Bn), para-tolyl (p-Tol), 2,6-diethylphenyl (detp), and 2,6-diisopropylphenyl (dipp)) have been generated by bibenzyl extrusion from Tp*2UBn. Tp*2U(NBn), Tp*2U(Np-Tol), and Tp*2U(Ndetp), along with previously reported Tp*2U(NPh) and Tp*2U(NAd) (Ad = 1-adamantyl), readily undergo [2π+2π] cycloaddition with isocyanates and isothiocyanates to generate κ2-ureato and κ2-thioureato derivatives, respectively. These new uranium(IV) complexes were characterized via multinuclear NMR, vibrational and electronic absorption spectroscopies, and, where possible, X-ray crystallography. The steric demands of the ligands were quantitatively assessed using computational modeling, and it was shown that cycloaddition only occurs for imido species where ligands occupy 90% or less of the coordination sphere.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b02547.

    • CIF data of 2-Bn (CIF)

    • CIF data of 2-dipp (CIF)

    • CIF data of 2-pTol (CIF)

    • CIF data of 2-detp (CIF)

    • CIF data of 3-Ph (CIF)

    • CIF data of 4-Ph (CIF)

    • CIF data of 5-Ph (CIF)

    • 1H NMR spectra, 11B NMR spectra, IR spectra, electronic absorption spectroscopy, and crystallographic details (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 23 publications.

    1. Nathan J. Lin, Diana Perales, Ellen M. Matson, Matthias Zeller, Suzanne C. Bart. Lewis Base Activation by Uranium(III) Complexes. Organometallics 2023, 42 (8) , 641-650. https://doi.org/10.1021/acs.organomet.2c00633
    2. Diana Perales, Nathan J. Lin, Michaela R. Bronstetter, Shannon A. Ford, Matthias Zeller, Suzanne C. Bart. Conversion of Uranium(III) Anilido Complexes to Uranium(IV) Imido Complexes via Hydrogen Atom Transfer. Organometallics 2022, 41 (5) , 606-616. https://doi.org/10.1021/acs.organomet.1c00680
    3. Diana Perales, Shannon A. Ford, Sahan R. Salpage, Tyler S. Collins, Matthias Zeller, Kenneth Hanson, Suzanne C. Bart. Conversion of Trivalent Uranium Anilido to Tetravalent Uranium Imido Species via Oxidative Deprotonation. Inorganic Chemistry 2020, 59 (17) , 11910-11914. https://doi.org/10.1021/acs.inorgchem.0c01704
    4. Caleb J. Tatebe, Ellen M. Matson, Christopher L. Clark, John J. Kiernicki, Phillip E. Fanwick, Matthias Zeller, Suzanne C. Bart. Low- and Mid-Valent Uranium Species Supported by Phenyltris(oxazolinyl)borate Ligands. Organometallics 2020, 39 (2) , 353-360. https://doi.org/10.1021/acs.organomet.9b00793
    5. Caleb J. Tatebe, John J. Kiernicki, Robert F. Higgins, Robert J. Ward, Sean N. Natoli, James C. Langford, Christopher L. Clark, Matthias Zeller, Paul Wenthold, Matthew P. Shores, Justin R. Walensky, Suzanne C. Bart. Investigation of the Electronic Structure of Aryl-Bridged Dinuclear U(III) and U(IV) Compounds. Organometallics 2019, 38 (5) , 1031-1040. https://doi.org/10.1021/acs.organomet.8b00794
    6. John J. Kiernicki, Caleb J. Tatebe, Matthias Zeller, and Suzanne C. Bart . Tailoring the Electronic Structure of Uranium Mono(imido) Species through Ligand Variation. Inorganic Chemistry 2018, 57 (4) , 1870-1879. https://doi.org/10.1021/acs.inorgchem.7b02791
    7. Congcong Zhang, Pikun Yang, Enwei Zhou, Xuebin Deng, Guofu Zi, and Marc D. Walter . Reactivity of a Lewis Base Supported Thorium Terminal Imido Metallocene toward Small Organic Molecules. Organometallics 2017, 36 (23) , 4525-4538. https://doi.org/10.1021/acs.organomet.7b00212
    8. Tongyu Li, Dongwei Wang, Yi Heng, Guohua Hou, Guofu Zi, Marc D. Walter. Reactivity of a Lewis base-supported uranium terminal imido metallocene towards small molecules. Dalton Transactions 2023, 455 https://doi.org/10.1039/D3DT02165C
    9. Diana Perales, Rina Bhowmick, Matthias Zeller, Pere Miro, Bess Vlaisavljevich, Suzanne C. Bart. Isolation of uranium( iii ) primary phosphido complexes. Chemical Communications 2022, 58 (69) , 9630-9633. https://doi.org/10.1039/D2CC02207A
    10. Pavel A. Zhizhko, Nikolai S. Bushkov, Andrey V. Pichugov, Dmitry N. Zarubin. Oxo/imido heterometathesis: From molecular stoichiometric studies to well-defined heterogeneous catalysts. Coordination Chemistry Reviews 2021, 448 , 214112. https://doi.org/10.1016/j.ccr.2021.214112
    11. Paul J. Fischer. Polypyrazolylborates and Scorpionates. 2021, 428-504. https://doi.org/10.1016/B978-0-08-102688-5.00072-6
    12. Sascha T. Löffler, Karsten Meyer. Actinides. 2021, 471-521. https://doi.org/10.1016/B978-0-12-409547-2.14754-7
    13. Michael A. Boreen, John Arnold. The synthesis and versatile reducing power of low-valent uranium complexes. Dalton Transactions 2020, 49 (43) , 15124-15138. https://doi.org/10.1039/D0DT03151H
    14. Christos Apostolidis, Attila Kovács, Olaf Walter, Eric Colineau, Jean‐Christophe Griveau, Alfred Morgenstern, Jean Rebizant, Roberto Caciuffo, Petra J. Panak, Thomas Rabung, Bernd Schimmelpfennig, Mauro Perfetti. Tris‐{hydridotris(1‐pyrazolyl)borato}actinide Complexes: Synthesis, Spectroscopy, Crystal Structure, Bonding Properties and Magnetic Behaviour. Chemistry – A European Journal 2020, 26 (49) , 11293-11306. https://doi.org/10.1002/chem.202001095
    15. Robert J. Ward, Pokpong Rungthanaphatsophon, Iker del Rosal, Steven P. Kelley, Laurent Maron, Justin R. Walensky. Divergent uranium- versus phosphorus-based reduction of Me 3 SiN 3 with steric modification of phosphido ligands. Chemical Science 2020, 11 (22) , 5830-5835. https://doi.org/10.1039/D0SC02261F
    16. Ekaterina N. Lapsheva, Thibault Cheisson, Carlos Álvarez Lamsfus, Patrick J. Carroll, Michael R. Gau, Laurent Maron, Eric J. Schelter. Reactivity of Ce( iv ) imido compounds with heteroallenes. Chemical Communications 2020, 56 (35) , 4781-4784. https://doi.org/10.1039/C9CC10052K
    17. Dorothea Schädle, Reiner Anwander. Rare-earth metal and actinide organoimide chemistry. Chemical Society Reviews 2019, 48 (24) , 5752-5805. https://doi.org/10.1039/C8CS00932E
    18. Caleb J. Tatebe, Tyler S. Collins, Grant Reed Barnett, Matthias Zeller, Suzanne C. Bart. Preparation of U(IV) κ1-amidinate complexes by nitrile metathesis. Polyhedron 2019, 158 , 1-7. https://doi.org/10.1016/j.poly.2018.10.042
    19. Frank T. Edelmann. Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2017. Coordination Chemistry Reviews 2018, 370 , 129-223. https://doi.org/10.1016/j.ccr.2018.05.013
    20. Michael A. Boreen, John Arnold. Multiple Bonding in Actinide Chemistry. 2018, 1-18. https://doi.org/10.1002/9781119951438.eibc2535
    21. Caleb J. Tatebe, Sara A. Johnson, Matthias Zeller, Suzanne C. Bart. Generation of Tp*2U(N3) from a family of new uranium(III) alkyl complexes. Journal of Organometallic Chemistry 2018, 857 , 152-158. https://doi.org/10.1016/j.jorganchem.2017.09.013
    22. Kimberly C. Mullane, Thibault Cheisson, Eiko Nakamaru‐Ogiso, Brian C. Manor, Patrick J. Carroll, Eric J. Schelter. Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion. Chemistry – A European Journal 2018, 24 (4) , 826-837. https://doi.org/10.1002/chem.201703396
    23. Caleb J. Tatebe, Kristen E. Gettys, Suzanne C. Bart. Reactivity of Actinide Imido Complexes. 2018, 1-42. https://doi.org/10.1016/bs.hpcre.2018.08.001
    Download PDF

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect