Ligand movement modulates the rate of proton transfer in reactions of [Fe4S4Cl4]2-.
Substitution of the first chloro-ligand in [Fe4S4Cl4]2- by 4-RC6H4S- (R = CF3, Cl, H, Me or MeO), in the presence of [H2N(CH2)3CH2]+, involves initial binding of thiolate, followed by protonation and finally chloride dissociation; the rate of protonation is facilitated by electron-withdrawing R-substituents indicating that Fe-thiolate bond length changes modulate proton transfer.
Dunford
Adrian J
AJ
Department of Chemistry, Bedson Building, University of Newcastle, Newcastle-upon-Tyne, UK NE1 7RU.
Henderson
Richard A
RA