Metal(IV) Complexes [M(LN,O,S)2]n (M = Ru, Os) of a Redox‐Active o‐Amidophenolate Ligand (LN,O,S)2– with Coordinating Thioether Appendix

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Abstract
Complexes [M(LN,O,S)2] [M = Ru, Os; (LN,O,S)2– = 4,6‐di‐tert‐butyl(2‐methylthiophenylamido)‐o‐phenolate] were obtained and structurally characterized as metal(IV) complexes with mer‐configured tridentate ligands. Two reversible oxidations and one (Os) or two (Ru) reversible reductions were investigated by EPR and UV/Vis/NIR spectroelectrochemistry. The first reduction leads to EPR‐silent MIII species, whereas the oxidation produces iminosemiquinone complexes with ligand‐centered spin and small‐metal participation at the singly occupied MO. Absorptions in the visible and near‐IR region are assigned with the help of time‐dependent (TD)‐DFT calculations.

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