The [Fe{(SePPh 2 ) 2 N} 2 ] Complex Revisited: X-ray Crystallography, Magnetometry, High-Frequency EPR, and Mössbauer Studies Reveal Its Tetrahedral Fe II Se 4 Coordination Sphere

Eleftherios Ferentinos (1) , Spyros Chatziefthimiou (2) , Athanassios K Boudalis (3) , Michael Pissas (2) , Guinevere Mathies (4) , Peter Gast (4) , Edgar J J Groenen (4) , Yiannis Sanakis (2) , Panayotis Kyritsis (1)

1 NKUA - National and Kapodistrian University of Athens
2 INN - Institute of Nanoscience and Nanotechnology "Demokritos" [Greece]
3 Institut de Chimie de Strasbourg
4 Universiteit Leiden = Leiden University

The synthesis and characterization of a preparation of the [Fe{(SePPh 2) 2 N} 2 ] complex (1 Td) is described. X-ray crystallography shows that this system contains a tetrahedral FeSe 4 coordination sphere. The structural features of 1 Td are compared with those of similar first row transition element complexes, including a recently reported preparation of [Fe{(SePPh 2) 2 N} 2 ] (1 SP) exhibiting a highly unusual square planar FeSe 4 coordination sphere. The electronic structure of 1 Td was elucidated by magnetometry, high-frequency EPR, and Mössbauer spectroscopic studies, which reveal zero-field splitting (ZFS) parameters typical of high spin S = 2 tetrahedral Fe II sites. Accurate ZFS parameters (D = +8.22 cm −1 , E/D = 0.104) were obtained by analysis of the EPR spectra and compared with those of the analogous [Fe{(SPPh 2) 2 N} 2 ] complex. The findings of this work call for a thorough structural and physicochemical characterization of the literature 1 SP system.

Domaines: Chimie de coordination

Eleftherios Ferentinos, Spyros Chatziefthimiou, Athanassios K Boudalis, Michael Pissas, Guinevere Mathies, et al.. The [Fe{(SePPh 2 ) 2 N} 2 ] Complex Revisited: X-ray Crystallography, Magnetometry, High-Frequency EPR, and Mössbauer Studies Reveal Its Tetrahedral Fe II Se 4 Coordination Sphere. European Journal of Inorganic Chemistry, 2018, 2018 (6), pp.713-721. ⟨10.1002/ejic.201701459⟩. ⟨hal-02444308⟩