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Protonation and substitution reactions of [{WFe3S4Cl3}2(μ-L)3]3- (L = SEt or OMe): quantifying how metal content and spectator ligands individually affect reactivity

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.

Publication metadata

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


DOI: 10.1039/b925835c


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