title: Unexpected formation of chiral pincer CNN nickel complexes with β-diketiminato type ligands via C-H activation: synthesis, properties, structures, and computational studies.
abstract: Reaction of lithiated chiral, unsymmetric β-diketimine type ligands HL(2a-e) containing oxazoline moiety (HL(2a-e) = 2-(2'-R(1)NH)-phenyl-4-R(2)-oxazoline) with trans-NiCl(Ph)(PPh(3))(2) afforded a series of new chiral CNN pincer type nickel complexes (3a-3e) via an unexpected cyclometalation at benzylic or aryl C-H positions. Single crystal X-ray diffraction analysis established the pincer coordination mode and the strained conformation. Chirality, and in one case, racemization of the target nickel complexes were confirmed by circular dichroism (CD) spectroscopy. Electronic structure and band assignments in experimental UV-vis and CD spectra were discussed on the basis of Density Functional Theory (DFT) and time-dependent (TD) DFT calculations.
authors: Department of Chemistry, University of North Dakota, 151 Cornell Street Stop 9024, Grand Forks, North Dakota 58202, USA.
authors: Zhengliang
authors: Z
authors: Lu
authors: Srinivas
authors: S
authors: Abbina
authors: Jared R
authors: JR
authors: Sabin
authors: Victor N
authors: VN
authors: Nemykin
authors: Guodong
authors: G
authors: Du
mesh_terms: D007097:Imines / Q000737:chemistry; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D007097:Imines; D008024:Ligands; D009942:Organometallic Compounds; D009532:Nickel