Molecules 2014, 19(4), 5301-5312; doi:10.3390/molecules19045301
Article

Identifying Stereoisomers by ab-initio Calculation of Secondary Isotope Shifts on NMR Chemical Shieldings

1email, 2email and 1,* email
Received: 27 February 2014; in revised form: 8 April 2014 / Accepted: 11 April 2014 / Published: 23 April 2014
(This article belongs to the Special Issue Isotope Effects)
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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.
Keywords: secondary isotope effects; NMR chemical shieldings; zero point vibrational effects; electronic structure calculations; ab-initio calculations
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MDPI and ACS Style

Böhm, K.-H.; Banert, K.; Auer, A.A. Identifying Stereoisomers by ab-initio Calculation of Secondary Isotope Shifts on NMR Chemical Shieldings. Molecules 2014, 19, 5301-5312.

AMA Style

Böhm K-H, Banert K, Auer AA. Identifying Stereoisomers by ab-initio Calculation of Secondary Isotope Shifts on NMR Chemical Shieldings. Molecules. 2014; 19(4):5301-5312.

Chicago/Turabian Style

Böhm, Karl-Heinz; Banert, Klaus; Auer, Alexander A. 2014. "Identifying Stereoisomers by ab-initio Calculation of Secondary Isotope Shifts on NMR Chemical Shieldings." Molecules 19, no. 4: 5301-5312.


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