NMR absolute shielding scales and nuclear magnetic dipole moments of transition metal nuclei. Issue 13 (20th March 2020)

• Record Type: Journal Article
• Authors: Antušek, Andrej; Repisky, Michal
• Is Part Of: Physical chemistry chemical physics. Volume 22:Issue 13(2020)
• Page Start: 7065
• Page End: 7076
• Publication Date: 2020-03-20
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d0cp00115e
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : This work reports new, accurate nuclear magnetic dipole moments for transition metal nuclei where the long-standing systematic error due to obsolete diamagnetic correction has been eliminated by ab initio calculations of NMR shielding constants. Abstract : This work reports new, accurate nuclear magnetic dipole moments for NMR-active transition metal nuclei where the long-standing systematic error due to obsolete diamagnetic correction has been eliminated by ab initio calculations of absolute NMR shielding constants. The error of the diamagnetic correction reaches ≈ −14 000 ppm for rhenium, which results in magnetic dipole moment corrections of about −3 × 10 −2 μ N for the 185 Re and 187 Re nuclei. Such extreme values are one to two orders of magnitude larger than the corrections reported in the literature so far. These findings may help to resolve discrepancies in hyperfine splitting experiments involving rhenium ions. To obtain the corrected transition metal nuclear magnetic dipole moments, NMR shielding constants for a series of transition metal complexes defined as NMR standards [Harris et al., Pure Appl. Chem., 2001, 73, 1795] were calculated using the non-relativistic coupled cluster method and four-component relativistic density functional theory. To reproduce the experimental conditions of the NMR standards, the solvent effects were incorporated by explicit and implicit solvent models.