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

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An Erratum to this article was published on 12 August 2011

Abstract

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, (R a )-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.

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Acknowledgments

Financial support (UBACYT X079 from the University of Buenos Aires and PIP0369 from CONICET) is gratefully acknowledged. SPAS acknowledges support from the Danish Center for Scientific Computing (DCSC) and the financial support from the Carlsberg Foundation and from the Danish Natural Science Research Council/The Danish Councils for Independent Research (grant number 272-08-0486).

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Authors and Affiliations

  1. Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and IFIBA, CONICET Ciudad Universitaria, Pabellon 1, 1428, Buenos Aires, Argentina

    Gabriel I. Pagola & Marta B. Ferraro

  2. Dipartimento di Chimica dell’Università degli Studi di Modena e Reggio Emilia, Via Campi 183, 41124, Modena, Italy

    Stefano Pelloni & Paolo Lazzeretti

  3. Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark

    Stephan P. A. Sauer

Authors
  1. Gabriel I. Pagola
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  2. Marta B. Ferraro
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  3. Stefano Pelloni
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  4. Paolo Lazzeretti
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  5. Stephan P. A. Sauer
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Corresponding author

Correspondence to Paolo Lazzeretti.

Additional information

Dedicated to Professor Pekka Pyykkö on the occasion of his 70th birthday and published as part of the Pyykkö Festschrift Issue.

Contribution to honor the scientific work and life of Prof. Pekka Pyykkö.

An erratum to this article can be found at http://dx.doi.org/10.1007/s00214-011-1017-6

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Pagola, G.I., Ferraro, M.B., Pelloni, S. et al. Electric field effects on nuclear spin–spin coupling tensors and chiral discrimination via NMR spectroscopy. Theor Chem Acc 129, 359–366 (2011). https://doi.org/10.1007/s00214-010-0851-2

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