Relativistic heavy-neighbor-atom effects on NMR shifts: Concepts and trends across the periodic table

Chemical shifts present crucial information about an NMR spectrum. They show the influence of the chemical environment on the nuclei being probed. Relativistic effects caused by the presence of an atom of a heavy element in a compound can appreciably, even drastically, alter the NMR shifts of the nearby nuclei. A fundamental understanding of such relativistic effects on NMR shifts is important in many branches of chemical and physical science. This review provides a comprehensive overview of the tools, concepts, and periodic trends pertaining to the shielding effects by a neighboring heavy atom in diamagnetic systems, with particular emphasis on the "spin-orbit heavy-atom effect on the light-atom"NMR shift (SO-HALA effect). The analyses and tools described in this review provide guidelines to help NMR spectroscopists and computational chemists estimate the ranges of the NMR shifts for an unknown compound, identify intermediates in catalytic and other processes, analyze conformational aspects and intermolecular interactions, and predict trends in series of compounds throughout the Periodic Table. The present review provides a current snapshot of this important subfield of NMR spectroscopy and a basis and framework for including future findings in the field. © 2020 American Chemical Society.Czech Science FoundationGrant Agency of the Czech Republic [18-05421S]; Ministry of Education, Youth, and Sports of the Czech RepublicMinistry of Education, Youth & Sports - Czech Republic [LQ1601, LO1504, LTAUSA19148]; Grant Agency of the Masaryk University [MUNI/E/1335/2019]; Slovak Grant Agency VEGAVedecka grantova agentura MSVVaS SR a SAV (VEGA) [2/0116/17, APVV-15-0726]; Slovak Grant Agency APVVSlovak Research and Development Agency [2/0116/17, APVV-15-0726]; Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence StrategyGerman Research Foundation (DFG) [EXC 2008/1-390540038]; DFG collaborative research centerGerman Research Foundation (DFG) [CRC1349, 387284271]; CESNET [LM2015042]; CERIT Scientific Cloud [LM2015085]; IT4Innovations National Supercomputing Center [LM2015070