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The Synthesis, Structures and Characterisation of New Mixed‐Ligand Manganese and Iron Complexes with Tripodal, Tetradentate Ligands
Author(s) -
van Gorkum Remy,
Berding Joris,
Mills Allison M.,
Kooijman Huub,
Tooke Duncan M.,
Spek Anthony L.,
Mutikainen Ilpo,
Turpeinen Urho,
Reedijk Jan,
Bouwman Elisabeth
Publication year - 2008
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.200701280
Subject(s) - chemistry , tripod (photography) , manganese , ligand (biochemistry) , metal , chelation , tripodal ligand , coordination complex , cyclic voltammetry , crystallography , infrared spectroscopy , metal ions in aqueous solution , inorganic chemistry , stereochemistry , crystal structure , electrochemistry , organic chemistry , biochemistry , physics , receptor , electrode , optics
The preparation of new manganese and iron complexes with the general formula [M(tripod)(anion)] is described, where M = Fe III or Mn III , “tripod” is a dianionic tetradentate tripodal ligand and the anion is a chelating β‐diketonate, 8‐oxyquinoline or acetate. The synthesis of this type of complexes was found to be straightforward, which allows for the preparation of a large variety of such coordination compounds. The complexes are characterised by X‐ray crystallography, infrared spectroscopy, UV/Vis spectroscopy, cyclic voltammetry and elemental analysis. A correlation between the ligand sets and the electron density at the metal centre in the complexes is proposed, based on the UV/Vis data and the CV measurements. The tripodal ligands are significant π‐donor ligands, and electron‐withdrawing or electron‐donating substituents on the phenolate arms were found to have a large influence on both the position of the d–d transitions in the UV/Vis spectra and the peak potentials in the CV measurements. The “secondary” β‐diketonate or acetate ligand does not have such a large effect on the electron density of the metal centre.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)