title: Neutral and cationic chiral NCN pincer nickel(II) complexes with 1,3-bis(2'-imidazolinyl)benzenes: synthesis and characterization.
abstract: Chiral 1,3-bis(2'-imidazolinyl)benzenes 1a-e easily undergo direct nickelation at the C2 position of the central benzene ring via the C-H bond activation in the reaction with anhydrous NiCl(2) giving neutral NCN pincer nickel(II) complexes 2a-e in 40-87% yields. Treatment of the nickel pincers 2a or 2c with AgBF(4) in CH(3)CN-CH(2)Cl(2) afforded the cationic nickel pincers 3a or 3c in good yields. All the complexes were characterized by elemental analysis, (1)H, (13)C NMR, and IR spectra. Molecular structures of the neutral complexes 2a, 2b and 2c as well as the cationic complex 3c have been determined by X-ray single-crystal diffraction. The cationic nickel pincers 3 are found to be effective catalysts for the Michael addition of ethyl 2-cyanopropionate to methyl vinyl ketone in the presence of i-Pr(2)NEt base with a catalyst loading of 5 mol% even at -78 °C, producing the adduct in >99% yield after 24 h albeit with no ee.
authors.affiliation: Department of Chemistry, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Zhengzhou University, Zhengzhou, 450052, China.
authors.forename: Dan-Dan
authors.initials: DD
authors.lastname: Shao
authors.forename: Jun-Long
authors.initials: JL
authors.lastname: Niu
authors.forename: Xin-Qi
authors.initials: XQ
authors.lastname: Hao
authors.forename: Jun-Fang
authors.initials: JF
authors.lastname: Gong
authors.forename: Mao-Ping
authors.initials: MP
authors.lastname: Song