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Facile P−C/C−H Bond‐Cleavage Reactivity of Nickel Bis(diphosphine) Complexes
Author(s) -
Zhang Shaoguang,
Li Haixia,
Appel Aaron M.,
Hall Michael B.,
Bullock R. Morris
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601469
Subject(s) - cleavage (geology) , iminium , bond cleavage , hydride , chemistry , reactivity (psychology) , nickel , crystallography , crystal structure , ligand (biochemistry) , single bond , stereochemistry , metal , catalysis , materials science , organic chemistry , group (periodic table) , medicine , biochemistry , alternative medicine , receptor , pathology , fracture (geology) , composite material
Unusual cleavage of P−C and C−H bonds of the P 2 N 2 ligand, in heteroleptic [Ni(P 2 N 2 )(diphosphine)] 2+ complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C , P , P ‐tridentate coordination mode. The structures of both the heteroleptic [Ni(P 2 N 2 )(diphosphine)] 2+ complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P−C/C−H bond cleavage, which involves C−H bond cleavage, hydride rotation, Ni−C/P−H bond formation, and P−C bond cleavage.