Format

Send to

Choose Destination
Molecules. 2014 Apr 23;19(4):5301-12. doi: 10.3390/molecules19045301.

Identifying stereoisomers by ab-initio calculation of secondary isotope shifts on NMR chemical shieldings.

Author information

1
Max-Planck-Institute for Chemical Energy Conversion, Stiftstraße 34-36, D-45470 Mülheim an der Ruhr, Germany. karl-heinz.boehm@cec.mpg.de.
2
Institut für Chemie, Technische Universität Chemnitz, Straße der Nationen 62, D-09111 Chemnitz, Germany. klaus.banert@chemie.tu-chemnitz.de.
3
Max-Planck-Institute for Chemical Energy Conversion, Stiftstraße 34-36, D-45470 Mülheim an der Ruhr, Germany. alexander.auer@cec.mpg.de.

Abstract

We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

PMID:
24762967
PMCID:
PMC6271661
DOI:
10.3390/molecules19045301
[Indexed for MEDLINE]
Free PMC Article

Supplemental Content

Full text links

Icon for Multidisciplinary Digital Publishing Institute (MDPI) Icon for PubMed Central
Loading ...
Support Center