Articles producció científica> Química Física i Inorgànica

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

  • Dades identificatives

    Identificador: imarina:5130194
    Autors:
    Jongbloed, Linda S.Garcia-Lopez, Diegovan Heck, RichardSiegler, Maxime A.Carbo, Jorge J.van der Vlugt, Jarl Ivar
    Resum:
    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.
  • Altres:

    Autor segons l'article: Jongbloed, Linda S.; Garcia-Lopez, Diego; van Heck, Richard; Siegler, Maxime A.; Carbo, Jorge J.; van der Vlugt, Jarl Ivar;
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Carbó Martin, Jorge Juan
    Paraules clau: 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
    Resum: 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.
    Àrees temàtiques: 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
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: j.carbo@urv.cat
    Identificador de l'autor: 0000-0002-3945-6721
    Data d'alta del registre: 2024-09-07
    Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
    Enllaç font original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b01162
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referència a l'article segons font original: Inorganic Chemistry. 55 (16): 8041-8047
    Referència de l'ítem segons les normes 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
    DOI de l'article: 10.1021/acs.inorgchem.6b01162
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2016
    Tipus de publicació: Journal Publications
  • Paraules clau:

    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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