Facile P−C/C−H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes

Shaoguang Zhang; Haixia Li; Aaron M. Appel; Michael B. Hall; R. Morris Bullock

doi:10.1002/chem.201601469

Facile P−C/C−H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes

Shaoguang Zhang, Haixia Li, Aaron M. Appel, Michael B. Hall, R. Morris Bullock

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

Unusual cleavage of P−C and C−H bonds of the P₂N₂ligand, in heteroleptic [Ni(P₂N₂)(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(P₂N₂)(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.

Original language	English
Pages (from-to)	9493-9497
Number of pages	5
Journal	Chemistry - A European Journal
Volume	22
Issue number	28
DOIs	https://doi.org/10.1002/chem.201601469
Publication status	Published - Jul 4 2016

Keywords

C−H bond cleavage
P−C bond cleavage
density functional calculations
nickel
phosphines

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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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 P2N2ligand, in heteroleptic [Ni(P2N2)(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(P2N2)(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.",

keywords = "C−H bond cleavage, P−C bond cleavage, density functional calculations, nickel, phosphines",

author = "Shaoguang Zhang and Haixia Li and Appel, {Aaron M.} and Hall, {Michael B.} and Bullock, {R. Morris}",

note = "Funding Information: The research at Pacific Northwest National Laboratory (PNNL) was supported by the U.S. Department of Energy, Office of Science (Office of Basic Energy Sciences; Division of Chemical Sciences, Geosciences & Biosciences). The PNNL is operated by Battelle for the US Department of Energy. H.L. and M.B.H. thank the National Science Foundation (CHE-1300787) and the Welch Foundation (A-0648) for financial support and the Texas A&M Supercomputing Facility for providing computing resources.",

year = "2016",

month = jul,

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doi = "10.1002/chem.201601469",

language = "English",

volume = "22",

pages = "9493--9497",

journal = "Chemistry - A European Journal",

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publisher = "Wiley-VCH Verlag",

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T1 - Facile P−C/C−H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes

AU - Zhang, Shaoguang

AU - Li, Haixia

AU - Appel, Aaron M.

AU - Hall, Michael B.

AU - Bullock, R. Morris

N1 - Funding Information: The research at Pacific Northwest National Laboratory (PNNL) was supported by the U.S. Department of Energy, Office of Science (Office of Basic Energy Sciences; Division of Chemical Sciences, Geosciences & Biosciences). The PNNL is operated by Battelle for the US Department of Energy. H.L. and M.B.H. thank the National Science Foundation (CHE-1300787) and the Welch Foundation (A-0648) for financial support and the Texas A&M Supercomputing Facility for providing computing resources.

PY - 2016/7/4

Y1 - 2016/7/4

N2 - Unusual cleavage of P−C and C−H bonds of the P2N2ligand, in heteroleptic [Ni(P2N2)(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(P2N2)(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.

AB - Unusual cleavage of P−C and C−H bonds of the P2N2ligand, in heteroleptic [Ni(P2N2)(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(P2N2)(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.

KW - C−H bond cleavage

KW - P−C bond cleavage

KW - density functional calculations

KW - nickel

KW - phosphines

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