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Chemistry. 2016 Jul 4;22(28):9493-7. doi: 10.1002/chem.201601469. Epub 2016 Jun 7.

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

Author information

1
Pacific Northwest National Laboratory, P.O. Box 999, K2-12, Richland, WA, 99352, USA.
2
Department of Chemistry, Texas A&M University, College Station, TX, 77845, USA.
3
Department of Chemistry, Texas A&M University, College Station, TX, 77845, USA. mbhall@tamu.edu.
4
Pacific Northwest National Laboratory, P.O. Box 999, K2-12, Richland, WA, 99352, USA. morris.bullock@pnnl.gov.

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.

KEYWORDS:

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

PMID:
27189413
DOI:
10.1002/chem.201601469

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