Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine
View/ Open
Impact
Scholar |
Other documents of the author: Alfonso Padilla, Carmina; Beltrán Álvarez, Tomás Francisco; Feliz Rodríguez, Marta; Llusar, Rosa
Metadata
Show full item recordcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
INVESTIGACIONMetadata
Title
Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of PentafluoropyridineAuthor (s)
Date
2015-01Publisher
SpringerBibliographic citation
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.Type
info:eu-repo/semantics/articlePublisher version
http://link.springer.com/article/10.1007/s10876-014-0733-1Version
info:eu-repo/semantics/submittedVersionSubject
Abstract
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 [-]
Is part of
Journal of Cluster Science, 2015, vol. 26, no 1Rights
© Springer Science+Business Media New York 2014
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/openAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/openAccess
This item appears in the folowing collection(s)
- QFA_Articles [825]