RT journal article
T1 Water-Soluble Mo3S4 Clusters Bearing Hydroxypropyl Diphosphine Ligands: Synthesis, Crystal Structure, Aqueous Speciation, and Kinetics of Substitution Reactions
A1 García Basallote, Manuel
A1 Fernández-Trujillo Rey, María Jesús
A1 Pino-Chamorro, Jose Ángel
A1 F. Beltrán, Tomás
A1 Corao, Carolina
A1 Llusar, Rosa
A1 Sokolov, Maxim
A1 Vicent, Cristian
A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
AB The [Mo3S4Cl3(dhprpe)3]+ (1+) cluster cation has been prepared by reaction between Mo3S4Cl4(PPh3)3 (solvent)2 and the watersoluble 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 structurewith 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.
PB ACS Publications
YR 2012
FD 2012-06
LK http://hdl.handle.net/10498/20486
UL http://hdl.handle.net/10498/20486
LA eng
DS Repositorio Institucional de la Universidad de Cádiz
RD 15-nov-2026