Site specific ligand substitution in cubane-type Mo3FeS44+ clusters: Kinetics and mechanism of reaction and isolation of mixed ligand Cl/SPh complexes
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Otros documentos de la autoría: Algarra, Andrés G.; García Basallote, Manuel; Fernández-Trujillo, M. Jesús; Llusar, Rosa; Pino Chamorro, Jose Angel; Sorribes, Iván; Vicent Barrera, Cristian
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Título
Site specific ligand substitution in cubane-type Mo3FeS44+ clusters: Kinetics and mechanism of reaction and isolation of mixed ligand Cl/SPh complexesAutoría
Fecha de publicación
2010Editor
Royal Society of ChemistryCita bibliográfica
Dalton Transactions (2010), 39, 15, p. 3725-3735Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://pubs.rsc.org/en/content/articlelanding/2010/dt/b924801c#!divAbstractVersión
info:eu-repo/semantics/publishedVersionResumen
The synthesis, crystal structure and solution characterization of the cubane-type [Mo3(FeCl)S4(dmpe)3Cl3] (1) (dmpe = 1,2-bis(dimethylphophane-ethane)) cluster are reported and the ligand substitution processes of ... [+]
The synthesis, crystal structure and solution characterization of the cubane-type [Mo3(FeCl)S4(dmpe)3Cl3] (1) (dmpe = 1,2-bis(dimethylphophane-ethane)) cluster are reported and the ligand substitution processes of chloride by thiophenolate investigated. The kinetics and the intimate mechanism of these substitutions reveal that compound 1 undergoes a number of Fe and Mo site specific ligand substitution reactions in acetonitrile solutions. In particular, PhS− coordination at the tetrahedral Fe site proceeds in a single resolved kinetic step whereas such substitutions at the Mo sites proceed more slowly. The effect of the presence of acids in the reaction media is also investigated and reveals that an acid excess hinders substitution reactions both at the Fe and Mo sites; however, an acid-promoted solvolysis of the Fe–Cl bonds is observed. Electrospray ionization (ESI) and tandem (ESI-MS/MS) mass spectrometry allow the identification of all the reaction intermediates proposed on the basis of stopped-flow measurements. The distinctive site specific reactivity made it possible to isolate two new clusters of the Mo3FeS44+ family featuring mixed chlorine/thiophenolate ligands, namely Mo3S4(FeSPh)(dmpe)3Cl3 (2) and [Mo3S4(FeSPh)(dmpe)3(SPh)3] (3). A detailed computational study has also been carried out to understand the details of the mechanism of substitution at the M–Cl (M = Mo and Fe) bonds as well as the solvolysis at the Fe–Cl sites, with particular emphasis on the role of acids on the substitution process. The results of the calculations are in agreement with the experimental observations, thus justifying the non-existence of an accelerating effect of acids on the thiophenolate substitution reaction, which differs from previous proposals for the Fe4S4 and MoFe3S4 clusters and some related compounds. [-]
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