Water-Soluble Mo3S4 Clusters Bearing Hydroxypropyl Diphosphine Ligands: Synthesis, Crystal Structure, Aqueous Speciation, and Kinetics of Substitution Reactionss
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Otros documentos de la autoría: García Basallote, Manuel; Fernández-Trujillo, M. Jesús; Pino Chamorro, Jose Angel; Llusar, Rosa; Beltrán Álvarez, Tomás Francisco; Corao, Carolina; Sokolov, Maxim; Vicent Barrera, Cristian
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Título
Water-Soluble Mo3S4 Clusters Bearing Hydroxypropyl Diphosphine Ligands: Synthesis, Crystal Structure, Aqueous Speciation, and Kinetics of Substitution ReactionssAutoría
Fecha de publicación
2012-06Editor
ElsevierTipo de documento
info:eu-repo/semantics/bookVersión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
The [Mo3S4Cl3(dhprpe)3]+ (1+) cluster cation has been prepared by reaction between Mo3S4Cl4(PPh3)3 (solvent)2 and the water-soluble 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe, L) ligand. The crystal structure ... [+]
The [Mo3S4Cl3(dhprpe)3]+ (1+) cluster cation has been prepared by reaction between Mo3S4Cl4(PPh3)3 (solvent)2 and the water-soluble 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe, L) ligand. The crystal structure of [1]2[Mo6Cl14] has been determined by X-ray diffraction methods and shows the typical incomplete cuboidal structure with a capping and three bridging sulfides. The octahedral coordination around each metal center is completed with a chlorine and two phosphorus atoms of the diphosphine ligand. Depending on the pH, the hydroxo group of the functionalized diphosphine can substitute the chloride ligands and coordinate to the cluster core to give new clusters with tridentate deprotonated dhprpe ligands of formula [Mo3S4(dhprpe-H)3]+ (2+). A detailed study based on stopped-flow, 31P{1H} NMR, and electrospray ionization mass spectrometry techniques has been carried out to understand the behavior of acid–base equilibria and the kinetics of interconversion between the 1+ and the 2+ forms. Both conversion of 1+ to 2+ and its reverse process occur in a single kinetic step, so that reactions proceed at the three metal centers with statistically controlled kinetics. The values of the rate constants under different conditions are used to discuss on the mechanisms of opening and closing of the chelate rings with coordination or dissociation of chloride. [-]
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Inorg. Chem., 2012, 51 (12)Derechos de acceso
© 2012 American Chemical Society
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