Relativistic Effects from Heavy Main Group p-Elements on the NMR Chemical Shifts of Light Atoms: From Pioneering Studies to Recent Advances

Abstract

This review represents a compendium of computational studies of relativistic effects on the NMR chemical shifts of light nuclei caused by the presence of heavy main group p-block elements in molecules. The narration starts from a brief discussion of the relativistic theories and quantum chemical methods for the calculation of NMR chemical shifts at the relativistic level of the electronic theory. The main part of the review contains a survey on the relativistic calculations of NMR shielding constants of the most popular NMR-active light nuclei such as 1H, 13C, 19F, 29Si, 15N, and 31P of compounds containing heavy p-elements. A special focus is placed on the relativistic effects initiated by the 16th and 17th group elements. Different factors governing the behavior of the relativistic effects on the chemical shifts of light atoms are discussed. In particular, the stereochemistry of the relativistic “heavy atom on the light atom” effect and the influence of the spin–orbit relativistic effects on the vibrational contributions to the shielding constants of light nuclei are considered.

Keywords

• NMR
• relativistic effects
• spin–orbit coupling
• NMR chemical shift
• NMR shielding constant
• heavy atom on light atom effect