A High-Frequency and High-Field EPR Study of New Azide and Fluoride Mononuclear Mn(III) Complexes

The isolation, structural characterization and electronic properties of three new six-coordinated
Mn(III) complexes, [Mn(bpea)(F)3] (1), [Mn(bpea)(N3)3] (2), and [Mn(terpy)(F)3] (3) are reported (bpea =
N,N-bis(2-pyridylmethyl)-ethylamine; terpy = 2,2‘:6‘,2‘ ‘-terpyridine). As for [Mn(terpy)(N3)3] (4) (previously
described by Limburg J.; Vrettos J. S.; Crabtree R. H.; Brudvig G. W.; de Paula J. C.; Hassan A.; Barra
A−L.; Duboc-Toia C.; Collomb M−N. Inorg. Chem. 2001, 40, 1698), all these complexes exhibit a Jahn−Teller distortion of the octahedron characteristic of high-spin Mn(III) (S = 2). The analysis of the
crystallographic data shows an elongation along the tetragonal axis of the octahedron for complexes 1
and 3, while complex 2 presents an unexpected compression. The electronic properties were investigated
using a high-field and high-frequency EPR study performed between 5 and 15 K (190−575 GHz). The
spin Hamiltonian parameters determined in solid state are in agreement with the geometry of the complexes
observed in the crystal structures. A negative D value found for 1 and 3 is related to the elongated tetragonal
distortion, whereas the positive D value determined for 2 is in accordance with a compressed octahedron.
The high E/D values, in the range of 0.103 to 0.230 for all complexes, are correlated with the highly distorted
geometry present around the Mn(III) ion. HF-EPR experiments were also performed on complex 1 in solution
and show that the D value is the only spin Hamiltonian parameter which is slightly modified compared to
the solid state (D = −3.67 cm-1 in solid state; D = −3.95 cm-1 in solution).