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Journal of Coordination Chemistry

Year: 2010  |  Volume: 63  |  Issue: 3  |  Page No.: 505 - 514

Synthesis, crystal structure, spectroscopy, and magnetism of a mixed valence Co(III)-Co(II)-Co(III) complex stabilized by N-(2-hydroxybenzyl)salicylaldimine

Chun Yang, Qing-Lun Wang, Guo-Tao Tang, Chao Wang, Shi-Ping Yan and Dai-Zheng Liao


Reaction of Co(OAc)2 · 4H2O with N-(2-hydroxybenzyl)salicylaldimine (H2La) in dimethylformamide (DMF)-H2O yields a linear trinuclear mixed valence complex [CoIII(μ-La)(μ-Lb)(μ-OAc)]2CoII · 2DMF (1). Here, HLb is salicylaldimine, which is afforded by an in situ transformation of H2La via cleavage of the C-N bond. Complex 1 has been characterized by X-ray crystallography as well as elemental analysis, UV-Vis, and IR spectroscopy. The cathodic and anodic responses of 1 in DMF appeared at -1.46 V (CoIII → CoII, quasi-irreversible) and +0.99 V (CoII → CoIII, irreversible) versus saturated calomel electrode, respectively. The magnetic behavior of 1 has been analyzed by the one-ion approximation with spin-orbit coupling in Oh symmetry giving λ = -121 cm-1.

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