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dc.contributor.authorF. Beltrán, Tomás
dc.contributor.authorPino-Chamorro, Jose Ángel
dc.contributor.authorFernández-Trujillo Rey, María Jesús 
dc.contributor.authorS. Safont, Vicent
dc.contributor.authorGarcía Basallote, Manuel 
dc.contributor.authorLlusar, Rosa
dc.contributor.otherCiencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánicaen_US
dc.date.accessioned2018-05-11T12:16:43Z
dc.date.available2018-05-11T12:16:43Z
dc.date.issued2015-12
dc.identifier.urihttp://hdl.handle.net/10498/20492
dc.description.abstractThe aminophosphine ligand (2-aminoethyl)- diphenylphosphine (edpp) has been coordinated to the W3(μ- S)(μ-S)3 cluster unit to afford trimetallic complex [W3S4Br3(edpp)3]+ (1+) in a one-step synthesis process with high yields. Related [W3S4X3(edpp)3]+ clusters (X = F−, Cl−, NCS−; 2+−4+) have been isolated by treating 1+ with the corresponding halide or pseudohalide salt. The structure of complexes 1+ to 4+ contains an incomplete W3S4 cubane-type cluster unit, and only one of the possible isomers is formed: the one with the phosphorus atoms trans to the capping sulfur and the amino groups trans to the bridging sulphurs. The remaining coordination position on each metal is occupied by X. Detailed studies using stopped-flow, 31P{1H} NMR, and ESI-MS have been carried out in order to understand the solution behavior and the kinetics of interconversion among species 1+, 2+, 3+, and 4+ in solution. Density functional theory (DFT) calculations have been also carried out on the reactions of cluster 1+ with the different anions. The whole set of experimental and theoretical data indicate that the actual mechanism of substitutions in these clusters is strongly dependent on the nature of the leaving and entering anions. The interaction between an entering F− and the amino group coordinated to the adjacent metal have also been found to be especially relevant to the kinetics of these reactions.en_US
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dc.language.isoengen_US
dc.publisherACS Publicationsen_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.sourceInorganic Chemistry 2015, 54, 607−618en_US
dc.titleSynthesis and Structure of Trinuclear W3S4 Clusters Bearing Aminophosphine Ligands and Their Reactivity toward Halides and Pseudohalidesen_US
dc.typeinfo:eu-repo/semantics/articleen_US
dc.identifier.doi10.1021/ic5025313


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