TY - JOUR
T1 - Electric field effects on nuclear spin-spin coupling tensors and chiral discrimination via NMR spectroscopy
AU - Pagola, Gabriel I.
AU - Ferraro, Marta B.
AU - Pelloni, Stefano
AU - Lazzeretti, Paolo
AU - Sauer, Stephan P. A.
PY - 2011/6/1
Y1 - 2011/6/1
N2 - Nuclear magnetic resonance spectrometers presently available are unable to recognize the two mirror-image forms of a chiral molecule, because in the absence of a chiral solvent, the NMR spectral parameters (chemical shifts and spin-spin coupling constants) are identical for the two enantiomers. This paper discusses how chirality may nevertheless, at least in theory, be recognized in liquid-state NMR spectroscopy by applying strong d. c. electric fields and measuring a pseudoscalar contribution to nuclear spin-spin coupling polarizability. Calculations are reported for medium-size chiral molecules, (2R)-N-methyloxaziridine, (Ra)-1,3-dimethylallene, and (2R)-2-methyloxirane. The very small contributions provided by the pseudoscalar of nuclear spin-spin coupling polarizability seem rather difficult to detect via NMR experiments in disordered phase.
AB - Nuclear magnetic resonance spectrometers presently available are unable to recognize the two mirror-image forms of a chiral molecule, because in the absence of a chiral solvent, the NMR spectral parameters (chemical shifts and spin-spin coupling constants) are identical for the two enantiomers. This paper discusses how chirality may nevertheless, at least in theory, be recognized in liquid-state NMR spectroscopy by applying strong d. c. electric fields and measuring a pseudoscalar contribution to nuclear spin-spin coupling polarizability. Calculations are reported for medium-size chiral molecules, (2R)-N-methyloxaziridine, (Ra)-1,3-dimethylallene, and (2R)-2-methyloxirane. The very small contributions provided by the pseudoscalar of nuclear spin-spin coupling polarizability seem rather difficult to detect via NMR experiments in disordered phase.
KW - Faculty of Science
KW - Quantum Chemistry
KW - NMR Spectroscopy
KW - chirality
KW - computational chemistry
U2 - 10.1007/s00214-010-0851-2
DO - 10.1007/s00214-010-0851-2
M3 - Journal article
SN - 1432-881X
VL - 129
SP - 359
EP - 366
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
IS - 3-5
ER -