Premium
Metal(IV) Complexes [M(L N,O,S ) 2 ] n (M = Ru, Os) of a Redox‐Active o ‐Amidophenolate Ligand (L N,O,S ) 2– with Coordinating Thioether Appendix
Author(s) -
Hübner Ralph,
Sarkar Biprajit,
Fiedler Jan,
Záliš Stanislav,
Kaim Wolfgang
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200225
Subject(s) - chemistry , electron paramagnetic resonance , redox , ligand (biochemistry) , metal , crystallography , ruthenium , stereochemistry , inorganic chemistry , catalysis , nuclear magnetic resonance , biochemistry , physics , receptor , organic chemistry
Abstract Complexes [M( L N,O,S ) 2 ] [M = Ru, Os; ( L N,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 M III 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.