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dc.contributor.authorGarcía Algarra, Andrés
dc.contributor.otherCiencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánicaen_US
dc.date.accessioned2018-05-07T07:28:23Z
dc.date.available2018-05-07T07:28:23Z
dc.date.issued2016
dc.identifier.urihttp://hdl.handle.net/10498/20453
dc.description.abstractThe mechanisms for H2 activation by [Cp*Mo]2(μ- S)2(μ-S2) (1-a, Cp* = pentamethylcyclopentadienyl) and its reaction product [Cp*Mo]2(μ-S)2(μ-SH)2 (2) have been investigated by DFT methods. The reaction of 1-a involves the homolytic addition of H2 to its μ-S ligands, followed by the cleavage of the S–S bond of the μ-S2 ligand in a subsequent step. Complex 2 can adopt five conformations that only differ in the stereochemistry of the μ-SH and μ-S ligands; although an isomer with adjacent μ-S ligands (2-a) is formed initially, it then isomerises into the experimentally observed 2-d. This species promotes H/ D scrambling in H2/D2 mixtures, and the mechanism of the process has also been studied. Notably, all of the computed pathways for the addition of D2 to 2-d present prohibitive barriers; instead, only those isomers with adjacent μ-S ligands are able to react further. The homolytic activation of D2 by these leads to isomers of [Cp2Mo2(μ-SH)2(μ-SD)2], the interconversion of which is the rate-determining step.en_US
dc.formatapplication/pdfen_US
dc.language.isoengen_US
dc.publisherWilleyen_US
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internacional*
dc.rightsinfo:eu-repo/semantics/openAccess
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.sourceEuropean Journal of Inorganic Chemistry 2016, 1886–1894en_US
dc.subjectDensity functional calculationsen_US
dc.subjectReaction mechanismsen_US
dc.subjectHomogeneous catalysisen_US
dc.subjectDihydrogenen_US
dc.subjectHydrogen activationen_US
dc.subjectMolybdenumen_US
dc.titleComputational Insights into the Mechanisms of H2 Activation and H2/D2 Isotope Exchange by Dimolybdenum Tetrasulfide Complexesen_US
dc.typeinfo:eu-repo/semantics/articleen_US
dc.identifier.doi10.1002/ejic.201600121


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Attribution-NonCommercial-NoDerivatives 4.0 Internacional
This work is under a Creative Commons License Attribution-NonCommercial-NoDerivatives 4.0 Internacional