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Gold-to-Boron Aryl Transfer from a T-Shaped Phosphine–Borane Gold(I) Complex

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  • معلومة اضافية
    • Contributors:
      Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA); Institut de Chimie de Toulouse (ICT); Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3); Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP); Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3); Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS); Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM); Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS); Université de Toulouse (UT)
    • بيانات النشر:
      HAL CCSD
      American Chemical Society
    • الموضوع:
      2021
    • Collection:
      Université Toulouse III - Paul Sabatier: HAL-UPS
    • نبذة مختصرة :
      International audience ; T-shaped gold(I) complexes with significant Au→B interactions were prepared from the phosphine–borane i-Pr2P(o-C6H4)BFXyl2 [Fxyl = 3,5-(F3C)2C6H3]. The (P,B)AuArF complex 4 [ArF = 4-(F3C)C6H4] was obtained by an indirect route involving ligand exchange from (ArO)3PAuArF3a [Ar = 2,4-(t-Bu)2C6H3]. A different outcome was observed with the analogous precursor (MeO)3PAuArF3b. Here, the phosphite remains bonded to gold, and the borane moiety abstracts the ArF group from gold to give the zwitterionic dicoordinate gold(I) complex 5. DFT calculations support a 2-step associative pathway for this gold-to-boron aryl transfer. It involves a square-planar gold(I) complex with enhanced Au→B interaction as key intermediate and proceeds via a 3-center transition state.
    • Relation:
      hal-03329016; https://univ-pau.hal.science/hal-03329016; https://univ-pau.hal.science/hal-03329016/document; https://univ-pau.hal.science/hal-03329016/file/OM%20B-aryl%20coupling%20%40%20Au%28I%29_I.pdf
    • الرقم المعرف:
      10.1021/acs.organomet.1c00364
    • Rights:
      info:eu-repo/semantics/OpenAccess
    • الرقم المعرف:
      edsbas.49A22A05