title: Spin-crossover in an iron(III)-bispidine-alkylperoxide system.
abstract: 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.
authors.affiliation: Anorganisch-Chemisches Institut,Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany.
authors.forename: Jochen
authors.initials: J
authors.lastname: Bautz
authors.forename: Peter
authors.initials: P
authors.lastname: Comba
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D003198:Computer Simulation; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D010545:Peroxides / Q000737:chemistry*; D011789:Quantum Theory; D012680:Sensitivity and Specificity; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D013059:Spectrum Analysis, Raman / Q000379:methods
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D005290:Ferric Compounds; D008024:Ligands; D010545:Peroxides; C495809:bispidine; D007501:Iron