Spin-crossover in an iron(III)-bispidine-alkylperoxide system |
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Authors: | Bautz Jochen Comba Peter Que Lawrence |
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Institution: | Anorganisch-Chemisches Institut,Universit?t Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany. |
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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. |
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