Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative 15N NMR and DFT Study

Danila B. Vasilchenko, Sergey V. Tkachev, Athanassios C. Tsipis

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

The accurate prediction of 15N nuclear magnetic resonance (NMR) chemical shifts for three sets of nitrato and mixed-ligand aquanitrato rhodium (9 complexes), palladium (11 complexes) and platinum (11 complexes) systems was achieved using density functional theory (DFT) calculations employing the GIAO-PBE0/ADZP(M)∪6-31+G(d)(E)/PCM (M = Rh, Pd, or Pt, E = main group element) computational protocol. A comparison of δcalcd 15N NMR chemical shifts with δexptl 15N NMR chemical shifts reveals that the DFT calculations correctly predict the division of signals into two groups, the first one involving the PdII, PtII, and RhIII nitrato complexes, and the second the PtIV and PdIV nitrato complexes. Hydrogen bonds and the number of nitrato ligands and their coordination mode remarkably affect the δcalcd 15N chemical shift. Generally, the experimentally observed chemical shifts are found in a sufficiently narrower range for each metal center in comparison to the calculated ones due to an averaging action of the outer-sphere interactions of complexes with external molecules of water and nitric acid.

Original languageEnglish
Pages (from-to)627-639
Number of pages13
JournalEuropean Journal of Inorganic Chemistry
Volume2018
Issue number5
DOIs
Publication statusPublished - 7 Feb 2018

Keywords

  • Density functional calculations
  • Nitrates
  • Palladium
  • Platinum
  • Rhodium
  • CHEMICAL-SHIFTS
  • NITRIC-ACID SOLUTIONS
  • CRYSTAL-STRUCTURE
  • WATER-EXCHANGE
  • NITRATE SOLUTIONS
  • SHIELDING CONSTANTS
  • BASIS-SETS
  • PT-195 NMR
  • DENSITY-FUNCTIONAL THEORY
  • FISSION PLATINOIDS

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