Distinct stepwise reduction of a nickel-nickel-bonded compound containing an α-diimine ligand: from perpendicular to coaxial structures.
作者： Qingsong Dong , Xiao-Juan Yang , Shida Gong , Qiong Luo , Qian-Shu Li
关键词: Stereochemistry 、 Chemistry 、 Coaxial 、 Ligand 、 Nickel 、 Crystallography 、 Metal 、 Diimine 、 Perpendicular 、 Sodium
摘要: A nickel-nickel-bonded complex, [{Ni(μ-L · - )} 2 ] (1; L=[(2,6-iPr C 6 H 3 )NC(Me)] ), was synthesized from reduction of the LNiBr precursor by sodium metal. Further controllable 1 with 1.0, 2.0 and 3.0 equiv Na, respectively, afforded singly, doubly, triply reduced compounds [Na(DME) ]·[{Ni(μ-L ](2; DME=1,2-dimethoxyethane), [Na-(Et O)]Na[(L )Ni-NiL (3), [Na(Et O)] Na[L Ni-NiL (4). Here L represents neutral ligand, denotes its radical monoanion, is dianion. All four feature a short Ni-Ni bond 2.2957(6) to 2.4649(8) Ǻ. Interestingly, they display two different structures: perpendicular (1 2) coaxial (3 4) structure, in which metal-metal axis or collinear axes adiimine ligands, respectively. The electronic structures, bonding nature, energetic comparisons structure types were investigated DFT computations.
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