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    Metal-Ligand Cooperative Reactivity in the (pseudo)-Dearomatized PNX(P) Systems: the Influence of the Zwitterionic Form in Dearomatized Pincer Complexes

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    Type
    Article
    Authors
    Goncalves, Theo
    Huang, Kuo-Wei cc
    KAUST Department
    Chemical Science Program
    Homogeneous Catalysis Laboratory (HCL)
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2017-09-14
    Online Publication Date
    2017-09-14
    Print Publication Date
    2017-09-27
    Permanent link to this record
    http://hdl.handle.net/10754/625752
    
    Metadata
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    Abstract
    The concept of aromaticity in pincer ligands and complexes was discussed in order to provide insights into their metal-ligand cooperative activities. The aromatic PNx(P) and dearomatized PNx(P)* pincer ligands and the corresponding transition metal complexes were studied with the nucleus-independent chemical shift (NICSzz), anisotropy of the current (induced) density (ACID), isochemical shielding surfaces (ICSSzz), harmonic oscillator model of aromaticity (HOMA), MCBO, Shannon aromaticity, and natural bond order (NBO) analyses. The study on the model systems showed that for the dearomatized species the decrease of the NICS(1)zz value comes with the larger contribution of the aromatic zwitterionic mesomeric form. In all examples, the incorporation of the metal center into the pincer ligand decreases the NICS(1)zz values. The DFT calculations support the dearomatized pyridine ring in PNP* or PNN* ligand indeed being nonaromatic, in contrast to the PN3(P)* ligand which has partial aromatic character due to the larger contribution of the zwitterionic resonance structure. The difference in aromaticity between the rings contributes to the thermodynamic balance of the metal ligand cooperative reactions, changing the energetics of the process when different dearomatized pincer ligands are used. This was further exemplified by aromaticity analysis of the heterolytic hydrogen cleavage reaction of ruthenium PNN complexes of Milstein and the PN3 of Huang, with similar geometries but distinctive thermodynamic preference.
    Citation
    Gonçalves TP, Huang K-W (2017) Metal–Ligand Cooperative Reactivity in the (Pseudo)-Dearomatized PNx(P) Systems: The Influence of the Zwitterionic Form in Dearomatized Pincer Complexes. Journal of the American Chemical Society 139: 13442–13449. Available: http://dx.doi.org/10.1021/jacs.7b06305.
    Sponsors
    We acknowledge the service of NOOR 2, Shaheen 2 High Performance Computing Facilities, and financial support from King Abdullah University of Science and Technology (KAUST).
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.7b06305
    PubMed ID
    28862844
    Additional Links
    http://pubs.acs.org/doi/abs/10.1021/jacs.7b06305
    http://pubs.acs.org/doi/abs/10.1021/jacs.7b06305
    ae974a485f413a2113503eed53cd6c53
    10.1021/jacs.7b06305
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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