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

作者：Vasilchenko Danila B^*; Tkachev Sergey V; Tsipis Athanassios C

来源：European Journal of Inorganic Chemistry, 2018, 2018(5): 627-639.

DOI：10.1002/ejic.201701140

• Palladium
• Rhodium
• Platinum
• Nitrates
• Density functional calculations

The accurate prediction of N-15 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)boolean OR 6-31+ G(d)(E)/PCM (M = Rh, Pd, or Pt, E = main group element) computational protocol. A comparison of delta(calcd) N-15 NMR chemical shifts with delta(exptl) N-15 NMR chemical shifts reveals that the DFT calculations correctly predict the division of signals into two groups, the first one involving the Pd-II, Pt-II, and Rh-III nitrato complexes, and the second the Pt-IV and Pd-IV nitrato complexes. Hydrogen bonds and the number of nitrato ligands and their coordination mode remarkably affect the delta(calcd) N-15 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.

• 出版日期2018-2-7