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

Abstract

Kinetic studies on the substitution reactions of the terminal chloro-ligands of [{WFe₃S₄Cl₃}₂(μ-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(μ-SEt)₃]³⁻ with those of the isostructural [{MoFe₃S₄Cl₃}₂(μ-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(μ-SEt)₃]³⁻ with those of [{WFe₃S₄Cl₃}₂(μ-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(μ-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.