J. Chem. Phys. 135, 104116 (2011)

DOI: 10.1063/1.3632086

Electric field effects on nuclear magnetic shielding of the 1:1 and 2:1 (homo and heterochiral) complexes of XOOX' (X, X' = H, CH3) with lithium cation and their chiral discrimination

The set of 1:1 and 2:1 complexes of XOOX′ (X, X′ = H, CH3) with lithium cation has been studied to determine if they are suitable candidates for chiral discrimination in an isotropic medium via nuclear magnetic resonance spectroscopy. Conventional nuclear magnetic resonance is unable to distinguish between enantiomers in the absence of a chiral solvent. The criterion for experimental detection is valuated by the isotropic part of nuclear shielding polarisability tensors, related to a pseudoscalar of opposite sign for two enantiomers. The study includes calculations at coupled Hartree-Fock and density functional theory schemes for 17O nucleus in each compound. Additional calculations for1H are also included for some compounds. A huge static homogeneous electric field, perpendicular to the magnetic field of the spectromer, as big as ≈1.7 × 108 V m−1 should be applied to observe a shift of ≈1 ppm for 17O magnetic shielding in the proposed set of complexes.