A High-Frequency and High-Field EPR Study of New Azide and Fluoride Mononuclear Mn(III) Complexes
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- 作者：Claire Mantel ; Alia K. Hassan ; Jacques Pé ; caut ; Alain Deronzier ; Marie-Noë ; lle Collomb ; and Carole Duboc-Toia
- 刊名：Journal of the American Chemical Society
- 出版年：2003
- 出版时间：October 8, 2003
- 年：2003
- 卷：125
- 期：40
- 页码：12337 - 12344
- 全文大小：158K
- 年卷期：v.125,no.40(October 8, 2003)
- ISSN：1520-5126
文摘
The isolation, structural characterization and electronic properties of three new six-coordinatedMn(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) (previouslydescribed by Limburg J.; Vrettos J. S.; Crabtree R. H.; Brudvig G. W.; de Paula J. C.; Hassan A.; BarraA-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 thecrystallographic data shows an elongation along the tetragonal axis of the octahedron for complexes 1and 3, while complex 2 presents an unexpected compression. The electronic properties were investigatedusing a high-field and high-frequency EPR study performed between 5 and 15 K (190-575 GHz). Thespin Hamiltonian parameters determined in solid state are in agreement with the geometry of the complexesobserved in the crystal structures. A negative D value found for 1 and 3 is related to the elongated tetragonaldistortion, 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 distortedgeometry present around the Mn(III) ion. HF-EPR experiments were also performed on complex 1 in solutionand show that the D value is the only spin Hamiltonian parameter which is slightly modified compared tothe solid state (D = -3.67 cm-1 in solid state; D = -3.95 cm-1 in solution).