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Lookup NU author(s): Brendan Garrett, Professor Richard Henderson
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Kinetic studies on the substitution reactions of the terminal chloro-ligands of [{WFe3S4Cl3}(2)(m-L)(3)](3-) (L = SEt or MeO) by PhS-in the presence of [NHEt3](+) or [pyrH](+) allow determination of the proton affinities and rates of PhS- and proton binding to the clusters. The behaviours of both clusters are similar and follow the same general kinetic characteristics established in earlier work for other synthetic Fe-S-based clusters. Comparison of the results obtained with [{WFe3S4Cl3}(2)(mu-SEt)(3)](3-) with those of the isostructural [{MoFe3S4Cl3}(2)(mu-SEt)(3)](3-) shows that changing a Mo for W in the cuboidal cluster framework has a large effect on the rates of binding of PhS- or a proton. In contrast, comparison of the results of [{WFe3S4Cl3}(2)(mu-SEt)(3)](3-) with those of [{WFe3S4Cl3}(2)(mu-OMe)(3)](3-) shows that changing the bridging ligands has only a small effect on the rates of binding of PhS- or a proton. The reactivities of [{MFe3S4Cl3}(2)(mu-L)(3)](3-) are inconsistent with the major influence of the metal or bridging ligands being electronic, and are more consistent with their modulating the ability of the cluster to undergo bond length reorganisation during binding of the nucleophile or proton.
Author(s): Garrett B, Henderson RA
Publication type: Article
Publication status: Published
Journal: Dalton Transactions
Year: 2010
Volume: 39
Issue: 19
Pages: 4586-4592
Print publication date: 12/04/2010
ISSN (print): 1477-9226
ISSN (electronic): 1477-9234
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/b925835c
DOI: 10.1039/b925835c
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