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

机译:双(二膦)镍配合物的简便P-C / C-H键断裂反应性

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摘要

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.
机译:在温和条件下在杂配[Ni(P2N2)(二膦)](2+)配合物中,P2N2配体的PC和CH键异常断裂,导致形成具有C,P,P-三齿亚基的亚硝酸nium基甲酸酯协调模式。杂合[Ni(P2N2)(二膦)](2+)配合物和所得亚胺基甲磺酸镍盐的结构均已通过NMR光谱和X射线单晶衍射分析表征。密度泛函理论(DFT)计算用于研究P-C / C-H键断裂的机理,涉及C-H键断裂,氢化物旋转,Ni-C / P-H键形成和P-C键断裂。

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