Mechanism of the catalytic gas-phase aldehyde production from trinuclear W3S4 complexes bearing W-OEt groups
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Other documents of the author: Beltrán Álvarez, Tomás Francisco; Feliz Rodríguez, Marta; Llusar, Rosa; Safont Villarreal, Vicent Sixte; Vicent Barrera, Cristian
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comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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http://dx.doi.org/10.1016/j.cattod.2011.05.017 |
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Title
Mechanism of the catalytic gas-phase aldehyde production from trinuclear W3S4 complexes bearing W-OEt groupsAuthor (s)
Date
2011Publisher
ElsevierISSN
0920-5861Type
info:eu-repo/semantics/articlePublisher version
http://www.sciencedirect.com/science/article/pii/S0920586111004287Version
info:eu-repo/semantics/publishedVersionSubject
Abstract
Collision induced dissociation experiments of the alkoxo [W3S4(dmpe)2(O)(OCH2CH3)]+ tungsten (IV) cation reveal that aldehyde elimination is the dominant reaction pathway. Complementary deuterium labelling experiments ... [+]
Collision induced dissociation experiments of the alkoxo [W3S4(dmpe)2(O)(OCH2CH3)]+ tungsten (IV) cation reveal that aldehyde elimination is the dominant reaction pathway. Complementary deuterium labelling experiments give support to a hydrogen transfer mechanism, where the hydrogen atom exclusively originates from the α-position of the alkoxo ligand. On the basis of DFT calculations, two competitive mechanisms are proposed: one of them involving a proton transfer from the α-position of the alkoxo ligand to an oxygen atom of the vicinal Wdouble bond; length as m-dashO group; the other corresponding to a hydride transfer mechanism from the α-position of the alkoxo ligand to the geminate tungsten center. The calculated energy profiles show that the former is thermodynamically favoured and the second is kinetically favoured, with small energy differences between the two reaction paths; in consequence, both mechanisms compete under our experimental conditions. The proton transfer mechanism occurs through a seven-membered transition state structure while hydride transfer takes place through a four-center structure defined by the metal and the oxygen, carbon and hydrogen atoms of the ethoxo group. [-]
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Catalysis Today (2011), vol. 177, no. 1Rights
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