A Series of Diamagnetic Pyridine Monoimine Rhenium Complexes with Different Degrees of Metal‐to‐Ligand Charge Transfer: Correlating 13C NMR Chemical Shifts with Bond Lengths in Redox‐Active Ligands

A set of pyridine monoimine (PMI) rhenium(I) tricarbonyl chlorido complexes with substituents of different steric and electronic properties was synthesized and fully characterized. Spectroscopic (NMR and IR) and single‐crystal X‐ray diffraction analyses of these complexes showed that the redox‐active PMI ligands are neutral and that the overall electronic structure is little affected by the choices of the substituent at the ligand backbone. One‐ and two‐electron reduction products were prepared from selected starting compounds and could also be characterized by multiple spectroscopic methods and X‐ray diffraction. The final product of a one‐electron reduction in THF is a diamagnetic metal–metal‐bonded dimer after loss of the chlorido ligand. Bond lengths in and NMR chemical shifts of the PMI ligand backbone indicate partial electron transfer to the ligand. Two‐electron reduction in THF also leads to the loss of the chlorido ligand and a pentacoordinate complex is obtained. The comparison with reported bond lengths and ¹³C NMR chemical shifts of doubly reduced free pyridine monoaldimine ligands indicates that both redox equivalents in the doubly reduced rhenium complex investigated here are located in the PMI ligand. With diamagnetic complexes varying over three formal reduction stages at the PMI ligand we were, for the first time, able to establish correlations of the ¹³C NMR chemical shifts with the relevant bond lengths in redox‐active ligands over a full redox series.