Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine
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Títol
Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of PentafluoropyridineAutoria
Data de publicació
2015-01Editor
SpringerCita bibliogràfica
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.Tipus de document
info:eu-repo/semantics/articleVersió de l'editorial
http://link.springer.com/article/10.1007/s10876-014-0733-1Versió
info:eu-repo/semantics/submittedVersionParaules clau / Matèries
Resum
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 [-]
Publicat a
Journal of Cluster Science, 2015, vol. 26, no 1Drets d'accés
© Springer Science+Business Media New York 2014
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info:eu-repo/semantics/openAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/openAccess
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