title: Giant spin-orbit effects on1H and13C NMR shifts for uranium(vi) complexes revisited: role of the exchange-correlation response kernel, bonding analyses, and new predictions.
abstract: Previous relativistic quantum-chemical predictions of unusually large1H and13C NMR chemical shifts for ligand atoms directly bonded to a diamagnetic uranium(vi) center (P. Hrobárik, V. Hrobáriková, A. H. Greif and M. Kaupp, Angew. Chem., Int. Ed., 2012, 51, 10884) have been revisited by two- and four-component relativistic density functional methods. In particular, the effect of the exchange-correlation response kernel, which had been missing in the previously used two-component version of the Amsterdam Density Functional program, has been examined. Kernel contributions are large for cases with large spin-orbit (SO) contributions to the NMR shifts and may amount to up to ∼30% of the total shifts, which means more than a 50 ppm difference for the metal-bonded carbon shifts in some extreme cases. Previous calculations with a PBE-40HF functional had provided overall reasonable predictions, due to cancellation of errors between the missing kernel contributions and the enhanced exact-exchange (EXX) admixture of 40%. In the presence of an exchange-correlation kernel, functionals with lower EXX admixtures give already good agreement with experiments, and the PBE0 functional provides reasonable predictive quality. Most importantly, the revised approach still predicts unprecedented giant1H NMR shifts between +30 ppm and more than +200 ppm for uranium(vi) hydride species. We also predict uranium-bonded13C NMR shifts for some synthetically known organometallic U(vi) complexes, for which no corresponding signals have been detected to date. In several cases, the experimental lack of these signals may be attributed to unexpected spectral regions in which some of the13C NMR shifts can appear, sometimes beyond the usual measurement area. An extremely large uranium-bonded13C shift above 550 ppm, near the upper end of the diamagnetic13C shift range, is predicted for a known pincer carbene complex. Bonding analyses allow in particular the magnitude of the SO shifts, and of their dependence on the functional, on the ligand position in the complex, and on the overall electronic structure to be better appreciated, and improved confidence ranges for predicted shifts have been obtained.
authors: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany. peter.hrobarik@tu-berlin.de martin.kaupp@tu-berlin.de.
authors: Anja H
authors: AH
authors: Greif
authors: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany. peter.hrobarik@tu-berlin.de martin.kaupp@tu-berlin.de.
authors: Peter
authors: P
authors: Hrobárik
authors: Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260, USA.
authors: Jochen
authors: J
authors: Autschbach
authors: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany. peter.hrobarik@tu-berlin.de martin.kaupp@tu-berlin.de.
authors: Martin
authors: M
authors: Kaupp