On the catalytic transfer hydrogenation of nitroarenes by a cubane-type Mo3S4 cluster hydride: disentangling the nature of the reaction mechanism
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Otros documentos de la autoría: Safont Villarreal, Vicent Sixte; Sorribes, Iván; Andres, Juan; Llusar, Rosa; Oliva, Mónica; Ryzhikov, Maxim
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Título
On the catalytic transfer hydrogenation of nitroarenes by a cubane-type Mo3S4 cluster hydride: disentangling the nature of the reaction mechanismAutoría
Fecha de publicación
2019Editor
Royal Society of ChemistryISSN
1463-9076; 1463-9084Cita bibliográfica
SAFONT, Vicent S., et al. On the catalytic transfer hydrogenation of nitroarenes by a cubane-type Mo 3 S 4 cluster hydride: disentangling the nature of the reaction mechanism. Physical Chemistry Chemical Physics, 2019, vol. 21, no 31, p. 17221-17231.Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
https://pubs.rsc.org/en/content/articlelanding/2019/cp/c9cp02633a#!divAbstractVersión
info:eu-repo/semantics/acceptedVersionPalabras clave / Materias
Resumen
Cubane-type Mo3S4 cluster hydrides decorated with phosphine ligands are active catalysts for the
transfer hydrogenation of nitroarenes to aniline derivatives in the presence of formic acid (HCOOH) and
triethylamine ... [+]
Cubane-type Mo3S4 cluster hydrides decorated with phosphine ligands are active catalysts for the
transfer hydrogenation of nitroarenes to aniline derivatives in the presence of formic acid (HCOOH) and
triethylamine (Et3N). The process is highly selective and most of the cluster species involved in the
catalytic cycle have been identified through reaction monitoring. Formation of a dihydrogen cluster
intermediate has also been postulated based on previous kinetic and theoretical studies. However,
the different steps involved in the transfer hydrogenation from the cluster to the nitroarene to finally
produce aniline remain unclear. Herein, we report an in-depth computational investigation into
this mechanism. Et3N reduces the activation barrier associated with the formation of Mo–HHOOCH
dihydrogen species. The global catalytic process is highly exergonic and occurs in three consecutive
steps with nitrosobenzene and N-phenylhydroxylamine as reaction intermediates. Our computational
findings explain how hydrogen is transferred from these Mo–HHOOCH dihydrogen adducts to nitrobenzene with the concomitant formation of nitrosobenzene and the formate substituted cluster. Then,
a b-hydride elimination reaction accompanied by CO2 release regenerates the cluster hydride. Two
additional steps are needed for hydrogen transfer from the dihydrogen cluster to nitrosobenzene and
N-phenylhydroxylamine to finally produce aniline. Our results show that the three metal centres in the
Mo3S4 unit act independently, so the cluster can exist in up to ten different forms that are capable of
opening a wide range of reaction paths. This behaviour reveals the outstanding catalytic possibilities of
this kind of cluster complexes, which work as highly efficient catalytic machines. [-]
Publicado en
Physical Chemistry Chemical Physics, 2019, vol. 21, no 31.Proyecto de investigación
PrometeoII/2014/022; UJI-B2016-25; UJI-B2017-44; ACOMP/2015/1202; CTQ2015-65207-PDerechos de acceso
This journal is © the Owner Societies 2019.
SAFONT, Vicent S., et al. On the catalytic transfer hydrogenation of nitroarenes by a cubane-type Mo 3 S 4 cluster hydride: disentangling the nature of the reaction mechanism. Physical Chemistry Chemical Physics, 2019, vol. 21, no 31, p. 17221-17231.<http://doi.org/10.1039/c9cp02633a>
-- Reproduced by permission of The Royal Society of Chemistry.
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