Sulfur‐linked Phenolates as Ligands for the Syntheses of Low‐Nuclearity Iron(III) Complexes

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Abstract
Exploiting thiacalix4arene and sulfur‐bridged bisphenolates as ligands for bioinorganic studies involving iron(III) requires the prior development of synthetic routes (varying substituents and reaction conditions) to construct complexes with low nuclearities and accessible coordination sites, which was in the focus of this investigation. Treating p‐tert‐butylthiacalix4arene (H4TC) and 1, 4‐dimethyl‐p‐tert‐butylthiacalix4arene (Me2H2TC) with Fe[N(SiMe3)2]3 yielded in the formation of the iron(III) complexes [(Me3SiTC)2Fe2] (1) and [(Me2TC)3Fe2] (3), respectively. While 1 is a sandwich compound, in 3 one [Me2TC]2– unit is bridging two [Me2TCFe]+ moieties. Employing thiobisphenolates as ligands it turned out, that in dependence on the residues R and the preparation method it is possible to selectively access sandwich, anionic or neutral complexes, which were shown to contain central high‐spin iron(III) atoms. The syntheses, structures, and electronic properties of three iron(III) bisphenolate complexes, [ClL2Fe]NEt3H (4), [MeLFeCl2]NEt3H (5), and [tBuLFeCl(thf)] (7) are discussed.

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