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Updated: Aug 30, 2025
Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
A Planar Nickelaspiropentane Complex with Magnesium-Based Metalloligands: Synthesis, Structure, and Synergistic
Yanping Cai1, Shengjie Jiang1, Thayalan Rajeshkumar2
1Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou215123, P. R. China.
Abstract:
The nature of transition-metal-olefin bonding has been explained by the Dewar-Chatt-Duncanson model within a continuum of two extremes, namely, a π-complex and a metallacyclopropane. The textbook rule suggests that a low-spin late-transition-metal-ethylene complex more likely forms a π-complex rather than a metallacyclopropane. Herein, we report a low-spin late-transition-metal-bis-ethylene complex forming an unprecedented planar metalla-bis-cyclopropane structure with magnesium-based metalloligands. Treatment of LMgEt (L = [(DippNCMe)2CH]-, Dipp = 2,6-Pr2C6H3) with Ni(cod)2 (cod = 1,5-cyclooctadiene) formed the heterotrimetallic complex (LMg)2Ni(C2H4)2, which features a linear Mg-Ni-Mg linkage and a planar coordination geometry at the nickel center. Both structural features and computational studies strongly supported the Ni(C2H4)2 moiety as a nickelaspiropentane. The exposure of (LMg)2Ni(C2H4)2 to 1 bar H2 at room temperature produced a four-hydride-bridged complex (LMg)2Ni(μ-H)4. The profile of H2 activation was elucidated by density functional theory calculations, which indicated a novel Mg/Ni cooperative activation mechanism with no oxidation occurring at the metal center, differing from the prevailing mono-metal-based redox mechanism. Moreover, the heterotrimetallic complex (LMg)2Ni(C2H4)2 catalyzed the hydrogenation of a wide range of unsaturated substrates under mild conditions.
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