Articles producció científica> Química Física i Inorgànica

Arene C(sp2)-H Metalation at NiII Modeled with a Reactive PONCPh Ligand

  • Identification data

    Identifier: imarina:5130194
    Authors:
    Jongbloed, Linda S.Garcia-Lopez, Diegovan Heck, RichardSiegler, Maxime A.Carbo, Jorge J.van der Vlugt, Jarl Ivar
    Abstract:
    Coordination of the reactive phosphinitopyridylphenyl PONCPh ligand LH to NiBr2 initially yields paramagnetic brown NiBr2(LH) (1), but addition of triethylamine results in fast and facile cyclometalation at NiII, giving NiBr(¿3-P,N,C-L) (2) as well-defined species. This is a rare example of direct cyclometalation at NiII from a C-H bond in a ligand structure other than encumbering ligands (e.g., ECE pincers). Diamagnetic yellow complex 2 reacts instantaneously with HBF4 to give purple [NiBr(¿3-P,N-LH)]BF4 (3). A very unusual (an)agostic Ni(CPh-H) interaction in the solid-state structure of 3 was unequivocally demonstrated using single-crystal X-ray crystallography and was interpreted by density functional theory calculations (quantum theory of atoms in molecules and electron localization function analysis). These compounds may be viewed as models for key intermediates in the Ni-catalyzed C-H functionalization of arenes.
  • Others:

    Author, as appears in the article.: Jongbloed, Linda S.; Garcia-Lopez, Diego; van Heck, Richard; Siegler, Maxime A.; Carbo, Jorge J.; van der Vlugt, Jarl Ivar;
    Department: Química Física i Inorgànica
    URV's Author/s: Carbó Martin, Jorge Juan
    Keywords: Ray crystal-structure Potential basis-sets Polarization functions Pincer complexes Paramagnetic-susceptibility P,n-phosphinopyridine ligands Nickel-complexes Molecular-orbital methods H bond activation C-h
    Abstract: Coordination of the reactive phosphinitopyridylphenyl PONCPh ligand LH to NiBr2 initially yields paramagnetic brown NiBr2(LH) (1), but addition of triethylamine results in fast and facile cyclometalation at NiII, giving NiBr(¿3-P,N,C-L) (2) as well-defined species. This is a rare example of direct cyclometalation at NiII from a C-H bond in a ligand structure other than encumbering ligands (e.g., ECE pincers). Diamagnetic yellow complex 2 reacts instantaneously with HBF4 to give purple [NiBr(¿3-P,N-LH)]BF4 (3). A very unusual (an)agostic Ni(CPh-H) interaction in the solid-state structure of 3 was unequivocally demonstrated using single-crystal X-ray crystallography and was interpreted by density functional theory calculations (quantum theory of atoms in molecules and electron localization function analysis). These compounds may be viewed as models for key intermediates in the Ni-catalyzed C-H functionalization of arenes.
    Thematic Areas: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: j.carbo@urv.cat
    Author identifier: 0000-0002-3945-6721
    Record's date: 2024-09-07
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b01162
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Inorganic Chemistry. 55 (16): 8041-8047
    APA: Jongbloed, Linda S.; Garcia-Lopez, Diego; van Heck, Richard; Siegler, Maxime A.; Carbo, Jorge J.; van der Vlugt, Jarl Ivar; (2016). Arene C(sp2)-H Metalation at NiII Modeled with a Reactive PONCPh Ligand. Inorganic Chemistry, 55(16), 8041-8047. DOI: 10.1021/acs.inorgchem.6b01162
    Article's DOI: 10.1021/acs.inorgchem.6b01162
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2016
    Publication Type: Journal Publications
  • Keywords:

    Chemistry (Miscellaneous),Chemistry, Inorganic & Nuclear,Inorganic Chemistry,Physical and Theoretical Chemistry
    Ray crystal-structure
    Potential basis-sets
    Polarization functions
    Pincer complexes
    Paramagnetic-susceptibility
    P,n-phosphinopyridine ligands
    Nickel-complexes
    Molecular-orbital methods
    H bond activation
    C-h
    Química
    Physical and theoretical chemistry
    Medicina i
    Materiais
    Interdisciplinar
    Inorganic chemistry
    General medicine
    Farmacia
    Engenharias iii
    Engenharias ii
    Engenharias i
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Chemistry, inorganic & nuclear
    Chemistry (miscellaneous)
    Biotecnología
    Astronomia / física
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