RT info:eu-repo/semantics/article
T1 Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach
A1 García Algarra, Andrés
A1 Pino-Chamorro, Jose Ángel
A1 A. Laricheva, Yuliya
A1 Guillamón, Eva
A1 Fernández-Trujillo Rey, María Jesús
A1 Bustelo, Emilio
A1 L. Gushchin, Artem
A1 Y. Shmelev, Nikita
A1 A. Abramov, Pavel
A1 N. Sokolov, Maxim
A1 Llusar, Rosa
A1 García Basallote, Manuel
A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
AB A heterocyclic ligand 4,40-di-tert-butyl-2,20-bipyridine (dbbpy) has been coordinated to the Mo3S4 cluster unit affording the complex [Mo3S4Cl3(dbbpy)3]+ ([1]+) in a one-step ligand-exchange protocol from [Mo3S4(tu)8(H2O)]Cl4 4H2O (tu = thiourea). The new cluster was isolated as [1]PF6 and [1]Cl salts in high yields and the crystal structure of the latter determined by X-ray analysis. The synthetic procedure was extended to tungsten to afford [W3S4Cl3(dbbpy)3]+ ([2]+). Kinetic and NMR studies show that [1]+ reacts with several alkynes to form dithiolene species via concerted [3+2] cycloaddition reactions whereas [2]+ remains inert under similar conditions. The different rates for the reactions of [1]+ are rationalised by computational (DFT) calculations, which show that the more electron-withdrawing the substituents of the alkyne the faster the reaction. The inertness of [2]+ is due to the endergonicity of its reactions, which feature DGr values systematically 5–7 kcal mol 1 more positive than for those of [1]+.
PB The Royal Society of Chemistry and Owner Societies
YR 2016
FD 2016
LK http://hdl.handle.net/10498/20490
UL http://hdl.handle.net/10498/20490
LA eng
DS Repositorio Institucional de la Universidad de Cádiz
RD 04-mar-2021