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. 2021, 60, 7, 4772-4778
RETURN TO ISSUEPREVArticleNEXT

Oxidative Addition of Hydridic, Protic, and Nonpolar E–H Bonds (E = Si, P, N, or O) to an Aluminyl Anion

Cite this: Inorg. Chem. 2021, 60, 7, 4772–4778
Publication Date (Web):March 16, 2021
https://doi.org/10.1021/acs.inorgchem.0c03735
Copyright © 2021 American Chemical Society
Request reuse permissions

    Article Views

    1201

    Altmetric

    -

    Citations

    17
    LEARN ABOUT THESE METRICS
    Read OnlinePDF (1 MB)
    Get e-Alerts
    Supporting Info (1)»
    SUBJECTS:

    Abstract

    Abstract Image

    The aluminyl anion K[Al(NONDipp)] {NONDipp = [O(SiMe2NDipp)2]2–; Dipp = 2,6-iPr2C6H3} engages in oxidative additions with the E–H (E = Si, P, N, or O) bonds of phenylsilane (PhSiH3), mesityl phosphane (MesPH2; Mes = 2,4,6-Me3C6H2), 2,6-di-iso-propylaniline (DippNH2), and 2,6-di-tert-butyl-4-methylphenol (ArOH). The resulting (hydrido)aluminate salts are formed regardless of the E–H bond polarity. All of the products were characterized by nuclear magnetic resonance and infrared spectroscopic techniques and single-crystal X-ray diffraction. This study highlights the versatility of aluminyl anions to activate hydridic, acidic, and (essentially) nonpolar E–H bonds.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03735.

    • NMR spectra (PDF)

    Accession Codes

    CCDC 2051790–2051793 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

    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 17 publications.

    1. Han-Ying Liu, Mary F. Mahon, Michael S. Hill. Aluminum–Boron Bond Formation by Boron Ester Oxidative Addition at an Alumanyl Anion. Inorganic Chemistry 2023, 62 (37) , 15310-15319. https://doi.org/10.1021/acs.inorgchem.3c02566
    2. Han-Ying Liu, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Ryan J. Schwamm. Seven-Membered Cyclic Diamidoalumanyls of Heavier Alkali Metals: Structures and C–H Activation of Arenes. Organometallics 2023, Article ASAP.
    3. Nery Villegas-Escobar, Preston R. Hoobler, Alejandro Toro-Labbé, Henry F. Schaefer, III. High-Level Coupled-Cluster Study on Substituent Effects in H2 Activation by Low-Valent Aluminyl Anions. The Journal of Physical Chemistry A 2023, 127 (4) , 956-965. https://doi.org/10.1021/acs.jpca.2c08403
    4. Gerd M. Ballmann, Matthew J. Evans, Thomas X. Gentner, Alan R. Kennedy, J. Robin Fulton, Martyn P. Coles, Robert E. Mulvey. Synthesis, Characterization, and Structural Analysis of AM[Al(NONDipp)(H)(SiH2Ph)] (AM = Li, Na, K, Rb, Cs) Compounds, Made Via Oxidative Addition of Phenylsilane to Alkali Metal Aluminyls. Inorganic Chemistry 2022, 61 (49) , 19838-19846. https://doi.org/10.1021/acs.inorgchem.2c03010
    5. Matthew J. Evans, Andrea O’Reilly, Mathew D. Anker, Martyn P. Coles. Trapping an Unusual Ring-Opened Product of THF within a Lithium Hydrido Aluminate. Organometallics 2022, 41 (19) , 2657-2661. https://doi.org/10.1021/acs.organomet.2c00329
    6. Bijoy Ghosh, Ashwini K. Phukan. Unravelling the Potential of Ylides in Stabilizing Low-Valent Group 13 Compounds: Theoretical Predictions of Stable, Five-Membered Group 13 (Aluminum and Gallium) Carbenoids Capable of Small-Molecule Activation. Inorganic Chemistry 2022, 61 (37) , 14606-14615. https://doi.org/10.1021/acs.inorgchem.2c01630
    7. Sumanta Banerjee, Gerd M. Ballmann, Matthew J. Evans, Andrea O'Reilly, Alan R. Kennedy, J. Robin Fulton, Martyn P. Coles, Robert E. Mulvey. Three Oxidative Addition Routes of Alkali Metal Aluminyls to Dihydridoaluminates and Reactivity with CO 2. Chemistry – A European Journal 2023, 69 https://doi.org/10.1002/chem.202301849
    8. Matthew J. Evans, Mathew D. Anker, Claire L. McMullin, Martyn P. Coles. Controlled reductive C–C coupling of isocyanides promoted by an aluminyl anion. Chemical Science 2023, 14 (23) , 6278-6288. https://doi.org/10.1039/D3SC01387A
    9. Martyn P. Coles, Matthew J. Evans. The emerging chemistry of the aluminyl anion. Chemical Communications 2023, 59 (5) , 503-519. https://doi.org/10.1039/D2CC05963K
    10. Han-Ying Liu, Michael S. Hill, Mary F. Mahon. Diverse reactivity of an Al( i )-centred anion towards ketones. Chemical Communications 2022, 58 (49) , 6938-6941. https://doi.org/10.1039/D2CC02333D
    11. Diego Sorbelli, Leonardo Belpassi, Paola Belanzoni. Unraveling differences in aluminyl and carbene coordination chemistry: bonding in gold complexes and reactivity with carbon dioxide. Chemical Science 2022, 13 (16) , 4623-4634. https://doi.org/10.1039/D2SC00630H
    12. Natalia Tiessen, Mira Keßler, Beate Neumann, Hans‐Georg Stammler, Berthold Hoge. Oxidative Addition von C−F‐Bindungen an das Silanid‐Anion [Si(C 2 F 5 ) 3 ] −. Angewandte Chemie 2022, 134 (17) https://doi.org/10.1002/ange.202116468
    13. Natalia Tiessen, Mira Keßler, Beate Neumann, Hans‐Georg Stammler, Berthold Hoge. Oxidative Additions of C−F Bonds to the Silanide Anion [Si(C 2 F 5 ) 3 ] −. Angewandte Chemie International Edition 2022, 61 (17) https://doi.org/10.1002/anie.202116468
    14. Thomas X. Gentner, Matthew J. Evans, Alan R. Kennedy, Sam E. Neale, Claire L. McMullin, Martyn P. Coles, Robert E. Mulvey. Rubidium and caesium aluminyls: synthesis, structures and reactivity in C–H bond activation of benzene. Chemical Communications 2022, 58 (9) , 1390-1393. https://doi.org/10.1039/D1CC05379E
    15. Matthew J. Evans, Mathew D. Anker, Claire L. McMullin, Sam E. Neale, Martyn P. Coles. Dihydrogen Activation by Lithium‐ and Sodium‐Aluminyls. Angewandte Chemie International Edition 2021, 60 (41) , 22289-22292. https://doi.org/10.1002/anie.202108934
    16. Matthew J. Evans, Mathew D. Anker, Claire L. McMullin, Sam E. Neale, Martyn P. Coles. Dihydrogen Activation by Lithium‐ and Sodium‐Aluminyls. Angewandte Chemie 2021, 133 (41) , 22463-22466. https://doi.org/10.1002/ange.202108934
    17. Jorge Juan Cabrera‐Trujillo, Israel Fernández. Factors Controlling the Aluminum(I)‐ meta ‐Selective C−H Activation in Arenes. Chemistry – A European Journal 2021, 27 (48) , 12422-12429. https://doi.org/10.1002/chem.202101944
    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