Combined kinetic and DFT studies on the stabilization of the pyramidal form of H3PO2 at the heterometal site of [Mo3M’S4(H2O)10]4+ clusters (M’= Pd, Ni)
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Otros documentos de la autoría: Algarra, Andrés G.; Fernández-Trujillo, M. Jesús; Safont Villarreal, Vicent Sixte; Hernández Molina, Rita; García Basallote, Manuel
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Mostrar el registro completo del ítemcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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Título
Combined kinetic and DFT studies on the stabilization of the pyramidal form of H3PO2 at the heterometal site of [Mo3M’S4(H2O)10]4+ clusters (M’= Pd, Ni)Autoría
Fecha de publicación
2009Editor
Royal Society of ChemistryISSN
1477-9226Cita bibliográfica
GARCÍA ALGARRA, Andrés, et al. Combined kinetic and DFT studies on the stabilization of the pyramidal form of H 3 PO 2 at the heterometal site of [Mo 3 M′ S 4 (H 2 O) 10] 4+ clusters (M′= Pd, Ni). Dalton Transactions, 2009, no 9, p. 1579-1586.Tipo de documento
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info:eu-repo/semantics/acceptedVersionResumen
Kinetic and DFT studies have been carried out on the reaction of the [Mo3M’S4(H2O)10]4+
clusters (M’= Pd, Ni) with H3PO2 to form the [Mo3M’(pyr-H3PO2)S4(H2O)9]4+ complexes, in
which the rare pyramidal form of H3PO2 ... [+]
Kinetic and DFT studies have been carried out on the reaction of the [Mo3M’S4(H2O)10]4+
clusters (M’= Pd, Ni) with H3PO2 to form the [Mo3M’(pyr-H3PO2)S4(H2O)9]4+ complexes, in
which the rare pyramidal form of H3PO2 is stabilized by coordination to the M’ site of the
clusters. The reaction proceeds with biphasic kinetics, both steps showing a first order
dependence with respect to H3PO2. These results are interpreted in terms of a mechanism that
involves an initial substitution step in which one tetrahedral H3PO2 molecule coordinates to
M’ through the oxygen atom of the P=O bond, followed by a second step that consists in
tautomerization of coordinated H3PO2 assisted by a second H3PO2 molecule. DFT studies
have been carried out to obtain information on the details of both kinetic steps, the major
finding being that the role of the additional H3PO2 molecule in the second step consists in
catalysing a hydrogen shift from phosphorus to oxygen in O-coordinated H3PO2, which is
made possible by its capability of accepting a proton from P-H to form H4PO2
+ and then
transfer it to the oxygen. DFT studies have been also carried out on the reaction at the Mo
centres to understand the reasons that make these metal centres ineffective for promoting
tautomerization [-]
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Dalton Transactions, 2009, n. 9Derechos de acceso
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