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Issue 9, 2016
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Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach

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Abstract

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]+.

Graphical abstract: Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach

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Publication details

The article was received on 07 Jun 2016, accepted on 25 Jul 2016 and first published on 26 Jul 2016


Article type: Paper
DOI: 10.1039/C6NJ01787H
Citation: New J. Chem., 2016,40, 7872-7880
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    Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach

    J. A. Pino-Chamorro, Y. A. Laricheva, E. Guillamón, M. J. Fernández-Trujillo, E. Bustelo, A. L. Gushchin, N. Y. Shmelev, P. A. Abramov, M. N. Sokolov, R. Llusar, M. G. Basallote and A. G. Algarra, New J. Chem., 2016, 40, 7872
    DOI: 10.1039/C6NJ01787H

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