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

J Am Chem Soc. 2010 Aug 4;132(30):10477-83. doi: 10.1021/ja103296g.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Ligands
  • Models, Molecular
  • Molecular Conformation
  • Nickel / chemistry*
  • Stereoisomerism

Substances

  • Ligands
  • Nickel