Khrizanforova Vera V, Fayzullin Robert R, Morozov Vladimir I, Gilmutdinov Ildar F, Lukoyanov Anton N, Kataeva Olga N, Gerasimova Tatiana P, Katsyuba Sergey A, Fedushkin Igor L, Lyssenko Konstantin A, Budnikova Yulia H
Arbuzov Institute of Organic and Physical Chemistry, Federal Research Center Kazan Scientific Center, Russian Academy of Sciences, Arbuzov Street, 8, 420088, Kazan, Russian Federation.
Institute of Physics, Kazan Federal University, Kremlevskaya Street, 18, 420008, Kazan, Russian Federation.
Chem Asian J. 2019 Sep 2;14(17):2979-2987. doi: 10.1002/asia.201900677. Epub 2019 Aug 9.
New nickel-based complexes of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) with BF counterion or halide co-ligands were synthesized in THF and MeCN. The nickel(I) complexes were obtained by using two approaches: 1) electrochemical reduction of the corresponding nickel(II) precursors; and 2) a chemical comproportionation reaction. The structural features and redox properties of these complexes were investigated by using single-crystal X-ray diffraction (XRD), cyclic voltammetry (CV), and electron paramagnetic resonance (EPR) and UV/Vis spectroscopy. The influence of temperature and solvent on the structure of the nickel(I) complexes was studied in detail, and an uncommon reversible solvent-induced monomer/dimer transformation was observed. In the case of the fluoride complex, the unpaired electron was found to be localized on the dpp-bian ligand, whereas all of the other nickel complexes contained neutral dpp-bian moieties.
在四氢呋喃（THF）和乙腈（MeCN）中合成了新型的1,2-双[(2,6-二异丙基苯基)亚氨基]苊烯（dpp-bian）与BF 抗衡离子或卤化物共配体的镍基配合物。通过两种方法获得镍（I）配合物：1）相应镍（II）前体的电化学还原；2）化学归中反应。利用单晶X射线衍射（XRD）、循环伏安法（CV）、电子顺磁共振（EPR）和紫外/可见光谱对这些配合物的结构特征和氧化还原性质进行了研究。详细研究了温度和溶剂对镍（I）配合物结构的影响，观察到一种罕见的可逆溶剂诱导的单体/二聚体转变。在氟化物配合物的情况下，发现未成对电子定域在dpp-bian配体上，而所有其他镍配合物都含有中性dpp-bian部分。
