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Synthesis, Structure, and Gas-Phase Fragmentation of Trinuclear Mo3S4 Clusters Bearing Aminophosphine Ligands: A Combined Experimental and Theoretical Study
dc.contributor.author | Beltrán Álvarez, Tomás Francisco | |
dc.contributor.author | Safont Villarreal, Vicent Sixte | |
dc.contributor.author | Llusar, Rosa | |
dc.date.accessioned | 2017-03-08T15:19:16Z | |
dc.date.available | 2017-03-08T15:19:16Z | |
dc.date.issued | 2016-10-05 | |
dc.identifier.citation | 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. 5171-5179 | ca_CA |
dc.identifier.uri | http://hdl.handle.net/10234/166580 | |
dc.description.abstract | 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. | ca_CA |
dc.description.sponsorShip | Financial support from the Spanish Ministerio de Economia y Competitividad (grants CTQ2011-23157, CTQ2012-36253-C03-02 and CTQ2015-65207-P), the Universitat Jaume I (research project P1.1B2013-40), and the Generalitat Valenciana (PrometeoII/2014/022 and ACOMP/2015/102) is gratefully acknowledged. The authors also thank the Serveis Centrals d'Instrumentació Cientifica (SCIC) of the Universitat Jaume I for providing us with the mass spectrometry, NMR and IR spectroscopic, and X-ray facilities, as well as the Servei d'Informàtica for providing computer time. T. B. thanks the Spanish Ministerio de Ciencia e Innovación (MICINN) for a doctoral fellowship (FPI) and gratefully acknowledges the financial support from the University of Liège and the EU through a Marie Curie BeIPD-COFUND-IPD postdoctoral fellowship programme (2014-2016). | ca_CA |
dc.format.extent | 9 p. | ca_CA |
dc.format.mimetype | application/pdf | ca_CA |
dc.language.iso | eng | ca_CA |
dc.publisher | Wiley | ca_CA |
dc.relation.isPartOf | European Journal of Inorganic Chemistry (2016), issue 32 | ca_CA |
dc.rights.uri | http://rightsstatements.org/vocab/CNE/1.0/ | * |
dc.subject | Gas-Phase Fragmentation | ca_CA |
dc.subject | Aminophosphine Ligands | ca_CA |
dc.subject | Unsaturated molybdenum/imine | ca_CA |
dc.subject | Proton transfer | ca_CA |
dc.subject | DFT calculations | ca_CA |
dc.title | Synthesis, Structure, and Gas-Phase Fragmentation of Trinuclear Mo3S4 Clusters Bearing Aminophosphine Ligands: A Combined Experimental and Theoretical Study | ca_CA |
dc.type | info:eu-repo/semantics/article | ca_CA |
dc.identifier.doi | http://dx.doi.org/10.1002/ejic.201600586 | |
dc.rights.accessRights | info:eu-repo/semantics/restrictedAccess | ca_CA |
dc.relation.publisherVersion | http://onlinelibrary.wiley.com/doi/10.1002/ejic.201600586/full | ca_CA |
dc.type.version | info:eu-repo/semantics/publishedVersion | ca_CA |
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