Reactions of M3Te74+ (M = Mo, W) clusters with electrophilic reagents: Chalcogen exchange in the Te2 ligand and the first complexes of (TeS)2−
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Mostrar el registro completo del ítemcomunitat-uji-handle:10234/9
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http://dx.doi.org/10.1016/j.poly.2009.07.061 |
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Título
Reactions of M3Te74+ (M = Mo, W) clusters with electrophilic reagents: Chalcogen exchange in the Te2 ligand and the first complexes of (TeS)2−Autoría
Fecha de publicación
2009Editor
ElsevierISSN
2775387Cita bibliográfica
Polyhedron, 28, 16, p. 3479-3484Tipo de documento
info:eu-repo/semantics/articleVersión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
Reactions of triangular telluride-bridged Mo and W clusters [M<sub>3</sub>(μ<sub>3</sub>-Te)(μ<sub>2</sub>-Te<sub>2</sub>)<sub>3</sub>(dtp)<sub>3</sub>]<sup>+</sup> (M = Mo, W; dtp = (EtO)<sub>2</sub>PS<sub>2</sub>) ... [+]
Reactions of triangular telluride-bridged Mo and W clusters [M<sub>3</sub>(μ<sub>3</sub>-Te)(μ<sub>2</sub>-Te<sub>2</sub>)<sub>3</sub>(dtp)<sub>3</sub>]<sup>+</sup> (M = Mo, W; dtp = (EtO)<sub>2</sub>PS<sub>2</sub>) with S<sub>2</sub>Cl<sub>2</sub> or Br<sub>2</sub> lead to Te/S exchange in the Te<sub>2</sub> ligands, with the formation of complexes with a novel TeS<sup>2-</sup> ligand. Reaction of [W<sub>3</sub>(μ<sub>3</sub>-Te)(μ<sub>2</sub>-Te<sub>2</sub>)<sub>3</sub>(dtp)<sub>3</sub>]<sup>+</sup> with Br<sub>2</sub> or S<sub>2</sub>Cl<sub>2</sub> gives a mixture of complexes formulated as [W<sub>3</sub>Te<sub>4.25</sub>S<sub>2.75</sub>(dtp)<sub>3</sub>]<sup>+</sup> and [W<sub>3</sub>Te<sub>4.30</sub>S<sub>2.70</sub>(dtp)<sub>3</sub>]<sup>+</sup>, respectively, on the basis of X-ray structural analysis. Reaction of the Mo homolog, namely [Mo<sub>3</sub>(μ<sub>3</sub>-Te)(μ<sub>2</sub>-Te<sub>2</sub>)<sub>3</sub>(dtp)<sub>3</sub>]<sup>+</sup>, with S<sub>2</sub>Cl<sub>2</sub> gives rise to [M{cyrillic}o{cyrillic}<sub>3</sub>Te<sub>4.74</sub>S<sub>2.26</sub>((EtO)<sub>2</sub>PS<sub>2</sub>)<sub>3</sub>]<sup>+</sup>. Electrospray ionization mass spectrometry (ESI-MS) complements the information gathered from X-ray analysis regarding the degree of Te by S substitution; moreover, detailed insights on the regioselectivity of such replacement are also obtained from ESI-MS analysis. These experimental evidences indicate that Te by S replacement in W complexes display high regioselectivity (as evidenced by the exclusive formation of a W<sub>3</sub>Te<sub>4</sub>S<sub>3</sub><sup>4+</sup> core), the equatorial Te ligands being preferentially replaced over the Te<sub>ax</sub> and μ<sub>3</sub>-Te ligands. Conversely, for the Mo homologs, a broad distribution of Mo<sub>3</sub>Te<sub>7-x</sub>S<sub>x</sub><sup>4+</sup> cluster species ranging from x = 0 to 6 is observed. Bond distance analysis as well as crystal packing trends as a function of the cluster core M<sub>3</sub>Te<sub>7-x</sub>S<sub>x</sub><sup>4+</sup> (M = Mo, W; x = 0-6) composition are also reported. © 2009 Elsevier Ltd. All rights reserved. [-]
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