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Updated: Aug 7, 2026

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes
Published on: February 27, 2017
Interpretation of conformational effects on 2-endo-norborneol by natural chemical shielding analysis
Peter R Seidl1, J Walkimar de M Carneiro, J Glauco R Tostes
1Universidade Federal do Rio de Janeiro, Escola de Química, Centro de Tecnologia, Bloco E, CEP 21949-900, Rio de Janeiro, RJ, Brazil. pseidl@eq.ufrj.br
Abstract:
This paper represents an extension of our work on the (1)H and (13)C NMR chemical shifts of norbornane and 2-endo-norborneol. NCS-NBO analysis was employed to probe contributions of bond orbitals and orbitals of lone pairs to nuclear shielding in conformers of the alcohol generated by rotation of the C-O bond. Variations in (1)H and (13)C chemical shifts with the dihedral angle are discussed in terms of Lewis and non-Lewis partitioning and their respective importance is evaluated. In addition to hyperconjugation of the lone pair in a p orbital of oxygen that was previously reported, a sizable participation of the lone pair which is in an sp orbital is also observed and their combined effect dominates the carbon chemical shifts of the C(1)-C(2)-OH and C(3)-C(2)-OH fragments. Both lone pairs on oxygen also contribute to localized, though-space effects on nuclei in the vicinity, these effects answering for the largest deviations in hydrogen chemical shifts on rotation around the C-O bond. On the other hand, for conformers in which nonbonded repulsions lead to distortions in the molecular framework, variations in chemical shifts may be attributed to angular effects.
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