The iron(II) complex of a tetradentate bispidine ligand with two tertiary amines and two pyridine groups (L = dimethyl [3,7-dimethyl-9,9'-dihydroxy-2,4-di-(2-pyridyl)-3,7-diazabicyclo nonan-1,5-dicaboxylate]) is oxidized with tert-butyl hydroperoxide to the corresponding end-on tert-butylperoxo complex [Fe(III)(L)(OOtBu)(X)]n+ (X = solvent, anion). UV-vis, resonance Raman, and EPR spectroscopy, as a function of the solvent, show that this is a spin-crossover compound. The experimentally observed Raman vibrations for both low-spin and high-spin isomers are in good agreement with those computed by DFT.
Spurenleser: Der Eisen(II)‐Komplex des Bispidinliganden L1 wird mit H2O2 zu [(L1)FeIV(OH)2]2+ (1, siehe Bild) mit mittlerem Spin oxidiert und bildet mit Olefinen cis‐Diole 2; der High‐Spin‐Ferrylkomplex [(L1)FeIVO(OH2)]2+ (3) führt zur Epoxidierung (4). Anhand von Produktverteilungen (Diol/Epoxid) und 18O‐Markierungsstudien wird ein Mechanismus entwickelt, der durch DFT‐Analysen vollkommen gestützt wird.
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