In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH
2paoH) in Fe-Co chemistry. The 1:1:3 Fe
III(NO
3)
3·9H
2O/Co
II(ClO
4)
2·6H
2O/NH
2paoH reaction mixture in MeOH gave complex [Co
III2Fe
III(NH
2pao)
6](ClO
4)
2(NO
3) (1) in ca. 55% yield, the cobalt(II) being oxidized to cobalt(III) under the aerobic conditions. The same complex was isolated using cobalt(II) and iron(II) sources, the oxidation now taking place at both metal sites. The structure of 1 contains two structurally similar, crystallographically independent cations [Co
III2Fe
III(NH
2pao)
6]
3+ which are strictly linear by symmetry. The central high-spin Fe
III ion is connected to each of the terminal low-spin Co
III ions through the oximato groups of three 2.1110 (Harris notation) NH
2pao
− ligands, in such a way that the six O atoms are bonded to the octahedral Fe
III center ({Fe
IIIO
6} coordination sphere). Each terminal octahedral Co
III ions is bonded to six N atoms (three oximato, three 2-pyridyl) from three NH
2pao
− groups ({Co
IIIN
6} coordination sphere). The IR and Raman spectra of the complex are discussed in terms of the coordination mode of the organic ligand, and the non-coordinating nature of the inorganic ClO
4− and NO
3− counterions. The UV/VIS spectrum of the complex in EtOH shows the two spin-allowed d-d transitions of the low-spin 3d
6 cobalt(III) and a charge-transfer NH
2pao
− → Fe
III band. The
δ and Δ
ΕQ 57Fe-Mössbauer parameter of 1 at 80 K show the presence of an isolated high-spin Fe
III center. Variable-temperature (1.8 K–300 K) and variable-field (0–7 T) magnetic studies confirm the isolated character of Fe
III. A critical discussion of the importance of NH
2paoH and its anionic forms (NH
2pao
−, NHpao
2−) in homo- and heterometallic chemistry is also attempted.
Full article