Variable magnetic interactions between S = 1/2 cation radical salts of functionalizable electron-rich dithiolene and diselenolene Cp2Mo complexes. - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2013

Variable magnetic interactions between S = 1/2 cation radical salts of functionalizable electron-rich dithiolene and diselenolene Cp2Mo complexes.

Résumé

A series of Cp(2)Mo(dithiolene) and Cp(2)Mo(diselenolene) complexes containing N-alkyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (R-thiazdt, R = Me, Et, CH(2)CH(2)OH) and N-alkyl-1,3-thiazoline-2-thione-4,5-diselenolate ligand (R-thiazds, R = Me, Et) have been synthesized. These heteroleptic molybdenum complexes have been characterized by electrochemistry, spectroelectrochemistry, and single crystal X-ray diffraction. They act as very good electron donor complexes with a first oxidation potential 200 mV lower than in the prototypical Cp(2)Mo(dmit) complex and exhibit almost planar MoS(2)C(2) (or MoSe(2)C(2)) metallacycles. All five complexes formed charge transfer salts with a weak (TCNQ) and a strong acceptor (TCNQF(4)), affording ten different charge-transfer salts, all with 1:1 stoichiometry. Crystal structure determinations show that the S/Se substitution in the metallacycle systematically affords isostructural salts, while the Cp(2)Mo(R-thiazdt) complexes with R equals ethyl or CH(2)CH(2)OH can adopt different structures, depending on the involvement of the hydroxyl group into intra- or intermolecular hydrogen bonding interactions. Magnetic susceptibility data of the salts are correlated with their structural organization, demonstrating that a face-to-face organization of the Me-thiazdt (or Me-thiazds) ligand favors a strong antiferromagnetic interaction, while the bulkier R = Et or R = CH(2)CH(2)OH substituents can completely suppress such intermolecular interactions, with the added contribution of hydrogen bonding to the solid state organization.
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Dates et versions

hal-00814483 , version 1 (17-04-2013)

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Talia Bsaibess, Michel Guerro, Yann Le Gal, Daad Sarraf, Nathalie Bellec, et al.. Variable magnetic interactions between S = 1/2 cation radical salts of functionalizable electron-rich dithiolene and diselenolene Cp2Mo complexes.. Inorganic Chemistry, 2013, 52 (4), pp.2162-73. ⟨10.1021/ic3025606⟩. ⟨hal-00814483⟩
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