Issue 4, 2021

Inverse halogen dependence in anion 13C NMR

Abstract

Halogens cause pronounced and systematic effects on the 13C NMR chemical shift (δ13C) of an adjacent carbon nucleus, usually leading to a decrease in the values across the halogen series. Although this normal halogen dependence (NHD) is known in organic and inorganic compounds containing the carbon atom in its neutral and cationic forms, information about carbanions is scarce. To understand how δ13C changes in molecules with different charges, the shielding mechanisms of CHX3, CX3+, and CX3 (X = Cl, Br, or I) systems are investigated via density functional theory calculations and further analyzed by decomposition into contributions of natural localized molecular orbitals. An inverse halogen dependence (IHD) is determined for the anion series as a result of the negative spin–orbit contribution instead of scalar paramagnetic effects. The presence of a carbon nonbonding orbital in anions allows magnetic couplings that generate a deshielding effect on the nucleus and contradicts the classical association between δ13C and atomic charge.

Graphical abstract: Inverse halogen dependence in anion 13C NMR

Supplementary files

Article information

Article type
Paper
Submitted
11 Nov 2020
Accepted
23 Dec 2020
First published
23 Dec 2020

Phys. Chem. Chem. Phys., 2021,23, 3019-3030

Inverse halogen dependence in anion 13C NMR

R. V. Viesser and C. F. Tormena, Phys. Chem. Chem. Phys., 2021, 23, 3019 DOI: 10.1039/D0CP05891B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements