Synthesis, Structure, and Gas-Phase Fragmentation of Trinuclear Mo3S4 Clusters Bearing Aminophosphine Ligands: A Combined Experimental and Theoretical Study
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Otros documentos de la autoría: Beltrán Álvarez, Tomás Francisco; Safont Villarreal, Vicent Sixte; Llusar, Rosa
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http://dx.doi.org/10.1002/ejic.201600586 |
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Título
Synthesis, Structure, and Gas-Phase Fragmentation of Trinuclear Mo3S4 Clusters Bearing Aminophosphine Ligands: A Combined Experimental and Theoretical StudyFecha de publicación
2016-10-05Editor
WileyCita bibliográfica
BELTRÁN ÁLVAREZ, Tomás Francisco; SAFONT VILLAREAL, Vicent Sixte; LLUSAR BARELLES, Rosa María. Synthesis, Structure, and Gas-Phase Fragmentation of Trinuclear Mo3S4 Clusters Bearing Aminophosphine Ligands: A Combined Experimental and Theoretical Study. European Journal of Inorganic Chemistry (2016), issue 32, pp. 5171-5179Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://onlinelibrary.wiley.com/doi/10.1002/ejic.201600586/fullVersión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
Aminophosphine [Mo3S4X3(edpp)3]+ cluster complexes, 1+ (X = Cl) and 2+ (X = Br) {edpp = (2-aminoethyl)diphenylphosphine} have been quantitatively prepared by treating the [Mo3S7X6]2– anion with the edpp ligand in a ... [+]
Aminophosphine [Mo3S4X3(edpp)3]+ cluster complexes, 1+ (X = Cl) and 2+ (X = Br) {edpp = (2-aminoethyl)diphenylphosphine} have been quantitatively prepared by treating the [Mo3S7X6]2– anion with the edpp ligand in a one-pot synthetic procedure. Alternatively, complexes 1+ and 2+ can be synthesized using polymeric {Mo3S7X4}n phases as metal precursors. Their crystal structures show the incomplete cubane-type Mo3S4 cluster core as well as the formation of a unique isomer in which the nitrogen atoms of the amino group and the halide atoms are located above the trimetallic plane. Gas-phase reactivity studies on complexes 1+ and 2+ show the subsequent elimination of neutral HX (X = Cl, Br) molecules under collision induced dissociation (CID) conditions. The fragmentation pattern of 1+ and 2+ in combination with gas-phase DFT calculations are contrary to the general ideas involving the hemilabile character of the aminophosphine ligands and give support to the formation of unsaturated molybdenum/imine Mo=NH species. On the basis of DFT calculations, two competitive mechanisms involving a proton transfer from the amino group to a halide ligand attached to the geminal or to the vicinal molybdenum center are proposed. The first mechanism, which is a proton transfer within the nitrogen and halogen atoms bound to the same metal atom, is energetically favored from a theoretical point of view. [-]
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European Journal of Inorganic Chemistry (2016), issue 32Derechos de acceso
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