Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine
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Otros documentos de la autoría: Alfonso Padilla, Carmina; Beltrán Álvarez, Tomás Francisco; Feliz Rodríguez, Marta; Llusar, Rosa
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Título
Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of PentafluoropyridineAutoría
Fecha de publicación
2015-01Editor
SpringerCita bibliográfica
ALFONSO, Carmina, et al. Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine. Journal of Cluster Science, 2015, vol. 26, no 1, p. 199-209.Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://link.springer.com/article/10.1007/s10876-014-0733-1Versión
info:eu-repo/semantics/submittedVersionPalabras clave / Materias
Resumen
Hydrido molybdenum and tungsten(IV) cluster cations of formula [M3S4H3(dppe)3]+ (dppe = 1,2-(bis)dimethylphosphinoethane), [Mo-1]+ (M = Mo) and [W-1]+ (M = W), have been isolated by reacting their halide precursors ... [+]
Hydrido molybdenum and tungsten(IV) cluster cations of formula [M3S4H3(dppe)3]+ (dppe = 1,2-(bis)dimethylphosphinoethane), [Mo-1]+ (M = Mo) and [W-1]+ (M = W), have been isolated by reacting their halide precursors with borohydride. Synthetic procedures have been optimized by appropriate choice of the solvent. Furthermore, [M3S4F3(dppe)3]+ fluorido cluster complexes, [Mo-2]+ (M = Mo) and [W-2]+ (M = W) have been prepared through halogen substitution reactions using an excess of cesium fluoride. The structures of [Mo-1]+ and [Mo-2]+ have been determined by single crystal X-ray diffraction experiments. These [M-1]+ hydrido and [M-2]+ fluorido clusters have been used as catalysts and precatalysts, respectively, in the catalytic hydrodefluorination (HDF) of pentafluoropyridine using HSiMe2Ph as hydrogen source. The reaction proceeds under microwave and reflux conditions to selectively afford 2,3,5,6-tetrafluoropyridine. The [W-1]+ hydrido cluster is the most efficient catalyst with turnover numbers of 124, while the [Mo-1]+ hydrido cluster reacts faster. Fluorido [Mo-2]+ and [W-2]+ complexes provide lower yields and turnover numbers. In general, the molybdenum and tungsten [M-1]+ and [M-2]+ diphosphino complexes are more efficient than their dmpe (1,2-(bis)dimethylphosphinoethano) analogues and activate pentafluoropyridine under softer conditions [-]
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Journal of Cluster Science, 2015, vol. 26, no 1Derechos de acceso
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