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
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
Entity: Universitat Rovira i Virgili
Journal publication year: 2016
Publication Type: Journal Publications
Repositori URV