Synthesis and chemical reactivity of an Fe(III) metallacrown-6 towards N-donor Lewis bases

The iron(III) 18-azametallacrown-6 [Fe(ashz)(EtOH)]6 (1) (ashz3 − = trianionic derivative of N-acetylsalicylhydrazide), prepared upon reaction of [Fe3(μ3-O)(Piv)6(H2O)3](Piv) (Piv = ButCOO−) with H3ashz, reacts with N-heterocyclic Lewis bases (B = pyridine, 4-methyl pyridine, 3-amino pyridine or imidazole), leading to the stable adducts [Fe(ashz)(B)]6 (2 to 5, respectively) upon replacement of the labile ethanol ligand. All the compounds were characterized by elemental analysis, IR and ESI–mass spectroscopies and, for complexes 1 and the 3-amino pyridine adduct 4, also by X-ray crystallography. In both 1 and 4, the stereochemistry of the ligand imposes a propeller configuration of the metal cation which exhibits alternating Λ/Δ forms.

Chemical reactivity of a Fe(III) 18-azametallacrown-6, [Fe(ashz)(EtOH)]6 (1) (ashz3 − = trianionic derivative of N-acetylsalicylhydrazide), towards N-heterocyclic Lewis bases (pyridine, 4-methyl pyridine, 3-amino pyridine or imidazole) is reported. A structural comparison between the precursor 1 and the 3-amino pyridine adduct complex 4 is presented.Figure optionsDownload as PowerPoint slideHighlights
► Synthesis of an iron(III) 18-azametallacrown-6, [Fe(ashz)(EtOH)]6, is reported.
► Chemical reactivity towards N-heterocyclic Lewis bases is studied.
► Labile ethanol ligands are easily replaced without affecting the metallacrown ring.
► Structural comparison between starting 18-azametallacrown-6 and an adduct is given.