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. 2025 Jan 8;12(1):241334.
doi: 10.1098/rsos.241334. eCollection 2025 Jan.

Unexpected stability of the iron(II) complex by an asymmetrical Schiff base from Fe(III): structure, magnetic and Mössbauer investigations

Dawit Tesfaye  1   2   3 , Mamo Gebrezgiabher  1   2 , Jonas Braun  4 , Taju Sani  1   2 , Sebastien Diliberto  5 , Pascal Boulet  5 , Nandakumar Kalarikkal  6 , Christopher E Anson  4 , Annie K Powell  4 , Madhu Thomas  1   2
Affiliations

Unexpected stability of the iron(II) complex by an asymmetrical Schiff base from Fe(III): structure, magnetic and Mössbauer investigations

Dawit Tesfaye et al. R Soc Open Sci. .

Abstract

The asymmetric Schiff base prepared in situ from ethylenediamine and pyridine-2-carboxaldehyde reacts with Fe(ClO4)3·6H2O to form the Fe(II) complex [FeL2](ClO4)2 with L = N,N-diethyl-N'-(pyridin-2-yl)methylene)ethane-1,2-diamine, where the Fe(III) starting material has been unexpectedly reduced to Fe(II). This complex was characterized by elemental analysis, infrared spectra, single crystal and powder X-ray diffraction measurements, variable temperature DC magnetic measurement and room temperature Mössbauer spectroscopy. The asymmetric ligand L coordinates in a tridentate fashion through its pyridyl, azomethine and amino nitrogen atoms, generating a distorted octahedral geometry around the central metal ion. Variable temperature magnetic studies and a Mössbauer measurement show that the iron is locked in the low spin Fe(II) states.

Keywords: Mössbauer spectroscopy; asymmetrical Schiff base; low spin Fe(II) complex.

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Conflict of interest statement

We declare we have no competing interests.

Figures

Scheme 1.
Scheme 1.
The ligand L = N.N-diethyl-N′-(pyridine-2-yl)methylene)ethane-1,2-diamine.
Labelled ball and stick drawing of the Fe(II) complex 1.
Figure 1.
Labelled ball and stick drawing of the Fe(II) complex 1. Colour code: Fe dark green; N blue; C grey; H light grey; Cl pale green and O red. Hydrogen bonds shown as purple dashed lines.
Scheme 2.
Scheme 2.
Synthetic route for the formation of [FeL2](ClO4)2
Zig-zag chain of Fe(II) complexes running parallel to the c-axis in the crystal structure of 1, showing the pairwise N–H∙∙∙O–Cl–O∙∙∙H–N linkages via the perchlorates.
Figure 2.
Zig-zag chain of Fe(II) complexes running parallel to the c-axis in the crystal structure of 1, showing the pairwise N–H∙∙∙O–Cl–O∙∙∙H–N linkages via the perchlorates. Only one of the disorder components of the second perchlorate is shown for clarity; hydrogen bonds are shown as purple dashed lines.
Room temperature 57Fe Mössbauer spectra of [FeL2](ClO4)2.
Figure 3.
Room temperature 57Fe Mössbauer spectra of [FeL2](ClO4)2.
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