title: High-Frequency (13)C and (29)Si NMR Chemical Shifts in Diamagnetic Low-Valence Compounds of Tl(I) and Pb(II): Decisive Role of Relativistic Effects.
abstract: The (13)C and (29)Si NMR signals of ligand atoms directly bonded to Tl(I) or Pb(II) heavy-element centers are predicted to resonate at very high frequencies, up to 400 ppm for (13)C and over 1000 ppm for (29)Si, outside the typical experimental NMR chemical-shift ranges for a given type of nuclei. The large (13)C and (29)Si NMR chemical shifts are ascribed to sizable relativistic spin-orbit effects, which can amount to more than 200 ppm for (13)C and more than 1000 ppm for (29)Si, values unexpected for diamagnetic compounds of the main group elements. The origin of the vast spin-orbit contributions to the (13)C and (29)Si NMR shifts is traced to the highly efficient 6p → 6p* metal-based orbital magnetic couplings and related to the 6p orbital-based bonding together with the low-energy gaps between the occupied and virtual orbital subspaces in the subvalent Tl(I) and Pb(II) compounds. New NMR spectral regions for these compounds are suggested based on the fully relativistic density functional theory calculations in the Dirac-Coulomb framework carefully calibrated on the experimentally known NMR data for Tl(I) and Pb(II) complexes.
authors.affiliation: Center of Polymer Systems, University Institute, Tomas Bata University in Zlín , Třída T. Bati, 5678, CZ-76001, Zlín, Czech Republic.
authors.forename: Jan
authors.initials: J
authors.lastname: Vícha
authors.affiliation: CEITEC - Central European Institute of Technology, Masaryk University , Kamenice 5/A4, CZ-62500 Brno, Czech Republic.
authors.forename: Radek
authors.initials: R
authors.lastname: Marek
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences , Flemingovo nam. 2, CZ-16610, Prague, Czech Republic.
authors.forename: Michal
authors.initials: M
authors.lastname: Straka