Iron(III) chloride-benzotriazole adducts with trigonal bipyramidal geometry: Spectroscopic, structural and catalytic studies

The reactions of FeCl3 with benzotriazole (btaH), 1-methylbenzotriazole (Mebta), 5,6-dimethylbenzotriazole (5,6Me(2)btaH) and 5-chlorobenzotriazole (5ClbtaH) were studied in non-polar solvents. The new solid complexes [FeCl3(btaH)(2)] (1), [FeCl3(Mebta)(2)] (2), [FeCl3(5,6Me(2)btaH)(2)] (3) and [FeCl3(5Clb-taH)(2)]center dot 2(5ClbtaH) (4) have been isolated. The structures of the complexes have been determined by single-crystal, X-ray crystallography. The structures of 1-4 consist of mononuclear, high-spin 5-coordinate molecules; in addition, the crystal structure of 4 contains two lattice 5ClbtaH molecules per [FeCl3(5Clb-taH)(2)] unit. The coordinated benzotriazole molecules behave as monodentate ligands with their ligated atom being the nitrogen of the position 3 of the azole ring. The geometry at iron(III) is trigonal bipyramidal with the chlorido ligands occupying the equatorial sites. The crystal structures of the complexes are stabilized by stacking interactions and H bonds (for 1, 3 and 4 only). The new complexes were characterized by elemental analyses, magnetic susceptibilities at room temperature and spectroscopic (IR, far-IR, solid-state electronic UV/VIS/near-IR, Fe-57-Mossbauer, EPR only for complex 4) methods. All data are discussed in terms of the nature of bonding and the known structures. Complexes 1, 2 and 4 have been tested as homogeneous (MeCN) oxidation catalysts in the presence of the "green" H2O2 oxidant; they display moderate to high catalytic activity in the oxidation of several alkenes, cyclohexane and n-hexane, which is described in detail. (C) 2013 Elsevier Ltd. All rights reserved.