o‐Iminobenzoquinone and o‐Iminobenzosemiquinonate Anion Radical Complexes of Rhodium and Ruthenium

2,4‐Di‐tert‐butyl‐N‐[2‐(phenylthio)]phenyl‐o‐iminobenzosemiquinonate anion radical (LSPhISQ·–) and o‐iminobenzoquinone (LSPhIQ) complexes of types cis‐[RhIII(LSPhISQ·–)(PPh3)Cl2] (1) and cis‐[RuII(LSPhIQ)(PPh3)Cl2] (2) are reported. The X‐ray bond parameters of 2, BS DFT calculations and variable‐temperature X‐band EPR spectra established the electronic states of 1–2. It was verified that 1 exhibits valence tautomeric equilibria of type [RhIII(LSPhISQ·–)(PPh3)Cl2] ⇌ [RhII(LSPhIQ)(PPh3)Cl2] (LSPhIQ = o‐iminobenzoquinone state of LSPhISQ·–) in solution. Complex 1 is unstable in moist solvent and undergoes hydrolytic C–N bond cleavage to afford [RhIII(LSPhNH2)(PPh3)Cl3] (3). In solids and frozen glasses of 1 and 2, the contributions of the “[MII(LSPhIQ)]” states are larger, whereas in fluid solutions the contributions of the “[MIII(LSPhISQ·–)]” states dominate. The contribution of the di‐radical state, cis‐[RuIII(LSPhISQ·–)(PPh3)Cl2], to 2 is relatively small.