title: Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes.
abstract: Unusual cleavage of P-C and C-H bonds of the P2 N2 ligand, in heteroleptic [Ni(P2 N2 )(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(P2 N2 )(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.
authors.affiliation: Pacific Northwest National Laboratory, P.O. Box 999, K2-12, Richland, WA, 99352, USA.
authors.forename: Shaoguang
authors.initials: S
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, TX, 77845, USA.
authors.forename: Haixia
authors.initials: H
authors.lastname: Li
authors.affiliation: Pacific Northwest National Laboratory, P.O. Box 999, K2-12, Richland, WA, 99352, USA.
authors.forename: Aaron M
authors.initials: AM
authors.lastname: Appel
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, TX, 77845, USA. mbhall@tamu.edu.
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall
authors.affiliation: Pacific Northwest National Laboratory, P.O. Box 999, K2-12, Richland, WA, 99352, USA. morris.bullock@pnnl.gov.
authors.forename: R Morris
authors.initials: RM
authors.lastname: Bullock
keywords: C−H bond cleavage; P−C bond cleavage; density functional calculations; nickel; phosphines