Autor según el artículo: Jongbloed, Linda S.; Garcia-Lopez, Diego; van Heck, Richard; Siegler, Maxime A.; Carbo, Jorge J.; van der Vlugt, Jarl Ivar;
Departamento: Química Física i Inorgànica
Autor/es de la URV: Carbó Martin, Jorge Juan
Palabras clave: 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
Resumen: 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.
Áreas temáticas: 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
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
Direcció de correo del autor: j.carbo@urv.cat
Identificador del autor: 0000-0002-3945-6721
Fecha de alta del registro: 2024-09-07
Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b01162
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Inorganic Chemistry. 55 (16): 8041-8047
Referencia 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 del artículo: 10.1021/acs.inorgchem.6b01162
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2016
Tipo de publicación: Journal Publications
Repositori URV