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    Barium-Catalysed Dehydrocoupling of Hydrosilanes and Borinic Acids: A Mechanistic Insight.

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    Name:
    Coz_et_al-2019-Chemistry_-_A_European_Journal.pdf
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    1.703Mb
    Format:
    PDF
    Description:
    Accepted manuscript
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    Type
    Article
    Authors
    Le Coz, Erwann
    Zhang, Ziyun
    Roisnel, Thierry
    Cavallo, Luigi cc
    Falivene, Laura cc
    Carpentier, Jean-François cc
    Sarazin, Yann cc
    KAUST Department
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2020-02-25
    Online Publication Date
    2020-02-25
    Print Publication Date
    2020-03-18
    Embargo End Date
    2021-02-26
    Submitted Date
    2019-10-29
    Permanent link to this record
    http://hdl.handle.net/10754/660449
    
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    Abstract
    Two very rare cases of barium boryloxides, the homoleptic [Ba(OB{CH(SiMe3)2}2)2⋅C7H8] and the heteroleptic [{LONO4}BaOB{CH(SiMe3)2}2] stabilised by the multidentate aminoetherphenolate {LONO4}−, are presented, and their structural properties are discussed. The electron-deficient [Ba(OB{CH(SiMe3)2}2)2⋅C7H8] shows, in particular, resilient η6-coordination of the toluene molecule. Together with its amido parents [Ba{N(SiMe3)2}2⋅thf2] and [Ba{N(SiMe3)2}2]2, this complex catalyses the fast and chemoselective dehydrocoupling of borinic acids R2BOH and hydrosilanes HSiR′3, yielding borasiloxanes R2BOSiR′3 in a controlled fashion. The assessment of substrate scope indicates that, for now, the reaction is limited to bulky borinic acids. Kinetic analysis shows that the rate-limiting step of the catalytic manifold traverses a dinuclear transition state. A detailed mechanistic scenario is proposed on the basis of DFT computations, the results of which are fully consistent with experimental data. It consists of a stepwise process with rate-determining nucleophilic attack of a metal-bound O-atom onto the incoming hydrosilane, involving throughout dinuclear catalytically active species.
    Citation
    Le Coz, E., Zhang, Z., Roisnel, T., Cavallo, L., Falivene, L., Carpentier, J., & Sarazin, Y. (2020). Barium-Catalysed Dehydrocoupling of Hydrosilanes and Borinic Acids: A Mechanistic Insight. Chemistry – A European Journal. doi:10.1002/chem.201904933
    Sponsors
    L.C., L.F. and Z.Z. thank the King Abdullah University of Science and Technology (KAUST) for supporting this work. For computer time, this research used the resources of the KAUST Super-computing Laboratory (KSL) at KAUST. E.L.C. thanks the Univer-sity of Rennes 1 for a PhD grant.
    Publisher
    Wiley
    Journal
    Chemistry (Weinheim an der Bergstrasse, Germany)
    DOI
    10.1002/chem.201904933
    10.1002/chem.202000478
    10.1002/chem.202000477
    Additional Links
    https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202000478
    ae974a485f413a2113503eed53cd6c53
    10.1002/chem.201904933
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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