Chem. J. Chinese Universities ›› 2021, Vol. 42 ›› Issue (3): 709.doi: 10.7503/cjcu20200475

• Inorganic Chemistry • Previous Articles     Next Articles

Atropisomerism and Magnetic Properties of an in situ Synthesized Chiral Nickel Complex

RUAN Zeyu, DU Shannan, HUANG Guozhang, TONG Mingliang, LIU Junliang()   

  1. MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,School of Chemistry,Sun Yat?Sen University,Guangzhou 510275,China
  • Received:2020-07-20 Online:2021-03-10 Published:2021-03-08
  • Contact: LIU Junliang E-mail:liujliang5@mail.sysu.edu.cn

Abstract:

Atropisomers refer to a subclass of chiral compounds that cannot be superposed with its mirror image. For a long time, chiral complexes play an important role in the fields of medicine, dyes, materials and natural products. Metal complexes as atropisomers have widespread applications in asymmetric catalysis. In contrast, fewer examples are known as obtaining atropisomers from achiral substrate, while it is even rarer to use non-axial-chirality ligand to achieve atropisomers. In general, acetonitrile is reactive inert and difficult to break the C—H bond in acetonitrile, so it is usually not a good nucleophilic reagent precursor. Activation of acetonitrile molecules assisting with transition-metal ions is an effective approach for introducing cyanomethyl groups. Herein we demonstrate a pair of atropisomers obtained through in?situ assembly under the coordination of NiII and KI, where the non-axial-chirality ligand dpkMeCN-H[dpkMeCN=cyanomethyl-di(pyridin-2-yl)methanol] containing a cyanomethyl group was introduced by the reaction with acetonitrile. From the magnetic measurements and analysis, the ferromagnetic coupling between two Ni ions was revealed. Accompanied with zero-field splitting from the distorted octahedral Ni ions, magnetic anisotropy was preserved for the chiral nickel complexes.

Key words: Chirality, Atropisomer, Cyanomethylation, Magnetism, Zero-field splitting

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