Electric field effects on nuclear spin-spin coupling tensors and chiral discrimination via NMR spectroscopy

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 -