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Use of a cubane-type Mo3CoS4 molecular cluster as paramagnetic unit in the synthesis of hybrid charge-transfer salts |
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| Authors: | Sebastian Krackl Antonio Alberola Gerd Meyer |
| Institution: | a Universität zu Köln, Department für Chemie, Institut für Anorganische Chemie, Greinstraße 6, D-50939 Köln, Germany b Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071 Castelló de la Plana, Spain c Serveis Centrals d’Instrumentació Científica, Universitat Jaume I, Av. Sos Baynat s/n, 12071 Castelló de la Plana, Spain |
| Abstract: | Selective substitution of the chlorine atom coordinated to cobalt in the paramagnetic Mo3(CoCl)S4(dmpe)3Cl3 (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 Mo3(CoI)S4(dmpe)3Cl3]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 Mo3CoS4 system. Metathesis of the 1]I salt with the paramagnetic nickel anionic dithiolate Ni(mnt)2]− (mnt = maleonitrilodithiolate) affords 1]2Ni(mnt)2]. The stoichiometry evidenced by X-ray analysis reveals that reduction of the Ni(mnt)2]− radical to the corresponding diamagnetic closed shell Ni(mnt)2]2− dianion, presumably via dismutation, has occurred during the metathesis process. The crystal structure of 1]2Ni(mnt)2] consists of Ni(mnt)2]2− dianions sandwiched by two cluster 1+ cations which yield {1+·Ni(mnt)2]2−·1+} subunits arranged along the crystallographic c axis. Magnetic susceptibility measurements for 1]2Ni(mnt)2] 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+ cation while the Ni(mnt)2 moiety does not contribute to the paramagnetism of the sample. |
| Keywords: | Cluster chalcogenides Magnetism Charge-transfer salts Nickel dithiolenes |
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