Unveiling the Importance of π-Stacking in Borrowing-Hydrogen Processes Catalysed by Iridium Complexes with Pyrene Tags
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http://dx.doi.org/10.1002/chem.201502948 |
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Títol
Unveiling the Importance of π-Stacking in Borrowing-Hydrogen Processes Catalysed by Iridium Complexes with Pyrene TagsData de publicació
2015-09-10Editor
WileyISSN
0947-6539Cita bibliogràfica
RUIZ‐BOTELLA, Sheila; PERIS, Eduardo. Unveiling the Importance of π‐Stacking in Borrowing‐Hydrogen Processes Catalysed by Iridium Complexes with Pyrene Tags. Chemistry–A European Journal, 2015, vol. 21, no 43, p. 15263-15271.Tipus de document
info:eu-repo/semantics/articleVersió de l'editorial
http://onlinelibrary.wiley.com/doi/10.1002/chem.201502948/fullParaules clau / Matèries
Resum
This work describes the preparation of a series of pyrene-tagged N-heterocyclic carbene complexes of iridium, and their use in two benchmark borrowing hydrogen reactions: the reduction of ketones by transfer hydroge ... [+]
This work describes the preparation of a series of pyrene-tagged N-heterocyclic carbene complexes of iridium, and their use in two benchmark borrowing hydrogen reactions: the reduction of ketones by transfer hydrogenation and the β-alkylation of secondary alcohols with primary alcohols. The detailed study of these homogeneously catalysed reactions reveals several important implications regarding the strong influence of the pyrene tags in the catalysts. First, the catalytic activity is partially inhibited by addition of an external amount of pyrene, but only when pyrene-tagged catalysts and aromatic substrates are used. Second, the rate order of the reaction is highly dependent on the nature of the substrates and the ligand. When pyrene-tagged catalysts and aromatic substrates are used, the reaction follows a zero-order dependence on the concentration of the substrate. All other combinations afford a second-order rate in the substrates. And third, the presence or absence of the pyrene functionality in the catalyst also influences the reaction order with respect to the concentration of the catalyst. Pyrene-containing catalysts display a fractional rate order of below 1. Finally, two pyrene-tagged catalysts were supported onto reduced-graphene oxide (rGO), and used as heterogeneous catalysts. While the dimetallic catalyst was effectively recycled 12 times, the monometallic catalyst maintained its activity for only three runs. [-]
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Chemistry–A European Journal, 2015, vol. 21, no 43Drets d'accés
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