Facile P−C/C−H Bond‐Cleavage Reactivity of Nickel Bis(diphosphine) Complexes |
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| Authors: | Dr Shaoguang Zhang Dr Haixia Li Dr Aaron M Appel Prof Michael B Hall Dr R Morris Bullock |
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| Institution: | 1. Pacific Northwest National Laboratory, Richland, WA, USA;2. Department of Chemistry, Texas A&M University, College Station, TX, USA |
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| Abstract: | Unusual cleavage of P?C and C?H bonds of the P2N2 ligand, 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. |
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| Keywords: | C− H bond cleavage density functional calculations nickel P− C bond cleavage phosphines |
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