Use of a cubane-type Mo3 CoS4 molecular cluster as paramagnetic unit in the synthesis of hybrid charge-transfer salts
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Altres documents de l'autoria: Krackl, Sebastian; Alberola Catalán, Antonio; Llusar, Rosa; Meyer, Gerd; Vicent Barrera, Cristian
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Mostra el registre complet de l'elementcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
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http://dx.doi.org/10.1016/j.ica.2010.06.029 |
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Títol
Use of a cubane-type Mo3 CoS4 molecular cluster as paramagnetic unit in the synthesis of hybrid charge-transfer saltsAutoria
Data de publicació
2010Editor
ElsevierISSN
201693Cita bibliogràfica
Inorganica Chimica Acta, 363, 15, p. 4197-4201Tipus de document
info:eu-repo/semantics/articleVersió
info:eu-repo/semantics/publishedVersionParaules clau / Matèries
Resum
Selective substitution of the chlorine atom coordinated to cobalt in the paramagnetic Mo<sub>3</sub>(CoCl)S<sub>4</sub>(dmpe)<sub>3</sub>Cl<sub>3</sub> (dmpe = 1,2-bis(dimethylphosphanyl) ethane) complex with a S = ... [+]
Selective substitution of the chlorine atom coordinated to cobalt in the paramagnetic Mo<sub>3</sub>(CoCl)S<sub>4</sub>(dmpe)<sub>3</sub>Cl<sub>3</sub> (dmpe = 1,2-bis(dimethylphosphanyl) ethane) complex with a S = 1/2 ground state has been achieved by iodine oxidation to afford the also paramagnetic [Mo<sub>3</sub>(CoI)S<sub>4</sub>(dmpe)<sub>3</sub>Cl<sub>3</sub>]I ([1]I) salt with a S = 1 ground state in almost quantitative yield. Replacement of chorine by iodine has no significant effect on the structural and electrochemical properties of the Mo<sub>3</sub>CoS<sub>4</sub> system. Metathesis of the [1]I salt with the paramagnetic nickel anionic dithiolate [Ni(mnt)<sub>2</sub>]<sup>-</sup> (mnt = maleonitrilodithiolate) affords [1]<sub>2</sub>[Ni(mnt)<sub>2</sub>]. The stoichiometry evidenced by X-ray analysis reveals that reduction of the [Ni(mnt)<sub>2</sub>]<sup>-</sup> radical to the corresponding diamagnetic closed shell [Ni(mnt)<sub>2</sub>]<sup>2-</sup> dianion, presumably via dismutation, has occurred during the metathesis process. The crystal structure of [1]<sub>2</sub>[Ni(mnt)<sub>2</sub>] consists of [Ni(mnt)<sub>2</sub>]<sup>2-</sup> dianions sandwiched by two cluster 1<sup>+</sup> cations which yield {1<sup>+</sup>·[Ni(mnt)<sub>2</sub>]<sup>2-</sup>·1<sup>+</sup>} subunits arranged along the crystallographic c axis. Magnetic susceptibility measurements for [1]<sub>2</sub>[Ni(mnt)<sub>2</sub>] show a χT product of 0.99 emu K/mol largely unchanged in the 10-300 K range. This behavior agrees with the presence of an S = 1 cluster 1<sup>+</sup> cation while the Ni(mnt)<sub>2</sub> moiety does not contribute to the paramagnetism of the sample. © 2010 Elsevier B.V. All rights reserved. [-]
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