Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach
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Other documents of the author: Pino Chamorro, Jose Angel; Laricheva, Yuliya A.; Guillamón, Eva; Fernández-Trujillo, M. Jesús; Bustelo, Emilio; Gushchin, Artem L.; Shmelev, Nikita Y.; Abramov, Pavel A.; Sokolov, Maxim; Llusar, Rosa; García Basallote, Manuel; Algarra, Andrés G.
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comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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Title
Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approachAuthor (s)
Date
2016Publisher
Royal Society of ChemistryISSN
1144-0546; 1369-9261Type
info:eu-repo/semantics/articleVersion
info:eu-repo/semantics/acceptedVersionAbstract
A heterocyclic ligand 4,4′-di-tert-butyl-2,2′-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) ... [+]
A heterocyclic ligand 4,4′-di-tert-butyl-2,2′-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 ΔGr values systematically 5–7 kcal mol−1 more positive than for those of [1]+. [-]
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New J. Chem., 2016, 40, 7872--7880Rights
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016.
PINO-CHAMORRO, Jose A., et al. Cycloaddition of alkynes to diimino Mo 3 S 4 cubane-type clusters: a combined experimental and theoretical approach. New Journal of Chemistry, 2016, vol. 40, no 9, p. 7872-7880. Http://dx.doi.org/10.1039/c6nj01787h. -
Reproduced by permission of The Royal Society of Chemistry.
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