Ridge-tile-like chiral topology: synthesis, resolution, and complete chiroptical characterization of enantiomers of edge-sharing binuclear square planar complexes of Ni(II) bearing achiral ligands.
Binuclear square planar Ni(II) complexes are described, formed by two tridentate ligands with two imine-nitrogens coordinating two nickel atoms. Such complexes are synthetically readily available with great structural variety and present new types of ridge-tile-like chiral compounds that are reasonably stable in the appropriate "bent" conformation. Enantiomerically pure samples of these compounds have been obtained for the first time using HPLC with a chiral stationary phase. Absolute configurations and chiroptical properties are fully characterized by ECD, VCD, ORD spectroscopy, and theoretical calculations. These new compounds with ridge-tile-like chiral topology are configurationally reasonably stable [DeltaG(double dagger) = 121.4 kJ mol(-1), t(1/2) = 14.9 h (78 degrees C, ethanol)], and therefore their chemistry, physical properties, and applications can be systematically studied.
Soloshonok
Vadim A
VA
Institute of Biorganic Chemistry and Petrochemistry, National Academy of Sciences of the Ukraine, Murmanska Street 1, Kyiv-94 02660, Ukraine. vadimsoloshonok@gmail.com
Ono
Taizo
T
Ueki
Hisanori
H
Vanthuyne
Nicolas
N
Balaban
Teodor Silviu
TS
Bürck
Jochen
J
Fliegl
Heike
H
Klopper
Wim
W
Naubron
Jean-Valère
JV
Bui
Tam T T
TT
Drake
Alex F
AF
Roussel
Christian
C
D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D013237:Stereoisomerism
D008024:Ligands; D009532:Nickel