Four‐component relativistic calculations of NMR shielding constants of the transition metal complexes. Part 1: Pentaammines of cobalt, rhodium, and iridium

• Published in: Magnetic resonance in chemistry 2022-04, Vol.60 (4), p.463-468
• Main Authors: Samultsev, Dmitry O., Semenov, Valentin A., Krivdin, Leonid B.
• Format: Article
• Language: English
• Subjects: 1H, 15N, 59Co, 103Rh, and 193IR NMR; Cobalt; Coordination compounds; Density functional theory; four‐component relativistic calculations; Iridium; Magnetic shielding; Mathematical analysis; NMR; Nuclear magnetic resonance; pentaammineaquacomplexes of cobalt(III); Relativistic effects; Rhodium; Rhodium isotopes; rhodium(III), iridium(III); Transition metal compounds
• ISSN: 0749-1581; 1097-458X
• DOI: 10.1002/mrc.5245

The nonrelativistic and four‐component fully relativistic calculations of 1H, 15N, 59Co, 103Rh, and 193Ir shielding constants of pentaammineaquacomplexes of cobalt(III), rhodium(III), and iridium(III) were carried out at the density functional theory (DFT) level of theory. The noticeable deshielding relativistic corrections were observed for nitrogen shielding constants (chemical shifts), whereas those corrections were found to be negligible for protons. For the transition metals cobalt, rhodium, and iridium, relativistic corrections to their nuclear magnetic resonance (NMR) shielding constants were found to be rather small for cobalt and rhodium (some 5–10%), whereas they are essentially larger for iridium (up to 70%). The nonrelativistic and four‐component fully relativistic calculations of 1H, 15N, 59Co, 103Rh, and 193Ir shielding constants of pentaammineaquacomplexes of cobalt (III), rhodium (III), and iridium (III) were carried out at the DFT level of theory. The noticeable deshielding relativistic corrections were observed for nitrogen shielding constants (chemical shifts), whereas those corrections were found to be negligible for protons.