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    Quantifying electronic similarities between NHC–gold(i) complexes and their isolobal imidazolium precursors

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    draft-CP-ART-05-2019-002844.pdf
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    Description:
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    Type
    Article
    Authors
    Azofra, Luis Miguel
    Veenboer, Richard M. P.
    Falivene, Laura
    Vummaleti, Sai V. C. cc
    poater, albert
    Nolan, Steven P.
    Cavallo, Luigi cc
    KAUST Department
    Chemical Science
    Chemical Science Program
    KAUST Catalysis Center
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2019
    Embargo End Date
    2020-07-14
    Permanent link to this record
    http://hdl.handle.net/10754/656011
    
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    Abstract
    A series of NHC–gold(I) (NHC = N-heterocyclic carbene) complexes has been studied by DFT calculations, enabling comparison of electronic and NMR behaviour with related protonated and free NHC molecules. Based on calculations, the NMR resonances of the carbenic C2 carbon atom in [Au(NHC)(Cl)] and [NHC(H)][Cl] exhibit increased shielding when compared to the free N-heterocyclic carbenes by an average of 46.6 ± 2.2 and 73.7 ± 4.3 ppm, respectively. A similar trend is observed when analysing the paramagnetic term of the magnetic shielding tensor. Although gold(I) and proton are considered isolobal fragments, imidazolium compounds lack π-backdonation due to the energetic unavailability of d-orbitals in H+. We propose that NHC–gold(I) complexes exhibit important π-backdonation irrespective of the relative amount of σ-donation between the NHC and gold(I)–X (X = anionic ligand) moieties in Au–NHC complexes. Interestingly, a correlation exists between the calculated shielding for gold (197Au) and the π-donation and π-backdonation contributions. We describe that this correlation also exists when analysing the σ-backdonation term, a property generally ignored yet representing a significant energetic contribution to the stability of the C2–Au bond.
    Citation
    Azofra, L. M., Veenboer, R. M. P., Falivene, L., Vummaleti, S. V. C., Poater, A., Nolan, S. P., & Cavallo, L. (2019). Quantifying electronic similarities between NHC–gold(i) complexes and their isolobal imidazolium precursors. Physical Chemistry Chemical Physics, 21(28), 15615–15622. doi:10.1039/c9cp02844g
    Sponsors
    L. M. A. is an ULPGC Postdoc Fellow, and thanks Universidad de Las Palmas de Gran Canaria (ULPGC). L. F., S. V. C. V., S. P. N. and L. C. acknowledge King Abdullah University of Science and Technology (KAUST) for support. R. M. P. V. and S. P. N. thank the European Research Council (ERC). A. P. is a Serra Húnter Fellow, and thanks the MICINN for the project PGC2018-097722-B-I00. We also thank the KAUST Supercomputing Laboratory, housing the supercomputer Shaheen II, for providing computational resources.
    Publisher
    Royal Society of Chemistry (RSC)
    Journal
    Physical Chemistry Chemical Physics
    DOI
    10.1039/c9cp02844g
    Additional Links
    http://xlink.rsc.org/?DOI=C9CP02844G
    ae974a485f413a2113503eed53cd6c53
    10.1039/c9cp02844g
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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