A high-frequency and high-field EPR study of new azide and fluoride mononuclear Mn(III) complexes

被引：0

作者：

Mantel, Claire ^{[1
,2
]}

Hassan, Alia K. ^{[1
]}

Pécaut, Jacques ^{[3
]}

Deronzier, Alain ^{[2
]}

Collomb, Marie-Noëlle ^{[2
]}

Duboc-Toia, Carole ^{[1
]}

机构：

[1] [1,Mantel, Claire

[2] Hassan, Alia K.

[3] Pécaut, Jacques

[4] Deronzier, Alain

[5] Collomb, Marie-Noëlle

[6] Duboc-Toia, Carole

来源：

Collomb, M.-N. (Marie-Noelle.Collomb@ujf-grenoble.fr) | 1600年 / American Chemical Society卷 / 125期

关键词：

Complexation - Crystal structure - Electronic properties - Manganese compounds - Paramagnetic resonance - X ray crystallography;

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摘要：

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).

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