| Abstract: | The computed chemical shifts of transition‐metal complexes with dimetridazole (= 1,2‐dimethyl‐5‐nitro‐1H‐imidazole; 1 ), a prototypical nitro‐imidazole‐based radiosensitizer, are reported at the GIAO‐BP86 and ‐B3LYP levels for BP86/ECP1‐optimized geometries. These complexes comprise MCl2( 1 )2] (M = Zn, Pd, Pt), RuCl2(DMSO)2( 1 )2], and Rh2(O2CMe)4( 1 )2]. Available δ(1H) and δ(15N) values, and Δδ(1H) and Δδ(15N) coordination shifts are well‐reproduced theoretically, provided solvation and relativistic effects are taken into account by means of a polarizable continuum model and suitable methods including spin–orbit (SO) coupling, respectively. These effects are particularly important for the metal‐coordinated N‐atom, where the contributions from solvation and relativity can affect δ(15N) and Δδ(15N) values up to 10–20 ppm. The 195Pt chemical shifts of cis‐ and trans‐PtCl2( 1 )2] are well‐reproduced using the zero‐order regular approximation including SO coupling (ZORA‐SO). Predictions are reported for 99Ru and 103Rh chemical shifts, which suggest that these metal centers could be used as additional, sensitive NMR probes in their complexes with nitro‐imidazoles. |
