Binding small molecules and ions to [Fe4S4Cl4](2-) modulates rate of protonation of the cluster

The mechanism of the acid-catalyzed substitution reaction of the terminal chloro-ligands in [Fe4S4Cl4](2-) by PhS(-) in the presence of NHBu(n)3(+) involves rate-limiting proton transfer from NHBu(n)3(+) to the cluster (k0 = 490 ± 20 dm(3) mol(-1) s(-1)). A variety of small molecules and ions (L = substrate = Cl(-), Br(-), I(-), RNHNH2 (R = Me or Ph), Me2NNH2, HCN, NCS(-), N3(-), Bu(t)NC or pyridine) bind to [Fe4S4Cl4](2-) and this affects the rate of subsequent protonation of [Fe4S4Cl4(L)](n-). Where the kinetics allow, the equilibrium constants for the substrates binding to [Fe4S4Cl4](2-) (K(L)) and the rates of proton transfer from NHBu(n)3(+) to [Fe4S4Cl4(L)](n-) (k) have been determined. The results indicate the following general features. (i) Bound substrates increase the rate of protonation of the cluster, but the rate increase is modest (k/k0 = 1.6 to ≥72). (ii) When K(L) is small, so is k/k0. (iii) Binding substrates which are good σ-donors or good π-acceptors lead to the largest k/k0. This behaviour is discussed in terms of the recent proposal that protonation of [Fe4S4Cl4](2-) at a μ3-S, is coupled to concomitant Fe-(μ3-SH) bond elongation/cleavage.