EPR and 1H NMR spectroscopy and DFT study of pentaammineruthenium(III)phenylcyanamide complexes

► Axial EPR signal observed for pentaammineurthenium(III) complexes of phenylcyanamide ligands. ► 1H NMR chemical shifts are consistent with spin density largely localized on Ru. ► Gas-phase DFT and DFT/PCM spin density calculations place too much spin density on the phenylcyanamide ligand. ► Solvent donor-acceptor interactions stabilize the Ru(III) oxidation state.