Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative 15N NMR and DFT Study. Issue 5 (29th January 2018)

• Record Type: Journal Article
• Authors: Vasilchenko, Danila B.; Tkachev, Sergey V.; Tsipis, Athanassios C.
• Is Part Of: European journal of inorganic chemistry. Issue 5(2018)
• Page Start: 627
• Page End: 639
• Publication Date: 2018-01-29
• Subjects: Palladium -- Rhodium -- Platinum -- Nitrates -- Density functional calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201701140
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The accurate prediction of 15 N 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 δ calcd 15 N NMR chemical shifts with δ exptl 15 N 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 δ calcd 15 N 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. Abstract : 15 N NMR spectroscopy data on aquanitrato complexes of palladium, rhodium and platinum are summarized. The dependence of nitrato ligands 15 N NMR chemical shifts on the nature of central ion and structure of the complexes are rationalized using DFT.