Kinetics and mechanism of the reactions of [FeCl4]- with PhS- or PhSH in MeCN, and the role of cations containing N-H groups.
The kinetics of the reactions between [FeCl4]- and an excess of PhS- have been studied using stopped-flow spectophotometry. The associated absorbance-time curves can be fitted to two exponentials, and these first and second phases correspond to the formation of [FeCl3(SPh)]- and [FeCl2(SPh)2]-, respectively. It seems likely that the steps involving formation of [FeCl(SPh)3]- and [Fe(SPh)4]- are associated with much smaller changes in absorbance and so are not detected. The kinetics of the first phase exhibit a non-linear dependence on the concentration of PhS- indicating an associative mechanism in which PhS- rapidly binds to [FeCl4]- to form [FeCl4(SPh)]2- prior to rate-limiting dissociation of chloride and formation of [FeCl3(SPh)]-. The kinetics indicate that at high concentrations of PhS-, the five-coordinate intermediate attains stoichiometric concentrations. This is confirmed by the spectroscopic changes. The second phase shows analogous kinetics. The kinetics of the reactions between [FeCl4]- and an excess of PhSH have also been studied. For the first phase the reaction occurs at a rate independent of the concentration of PhSH, consistent with an associative mechanism in which the solvent (MeCN) is the nucleophile to form [FeCl3(NCMe)]. Subsequent rapid replacement of the coordinated solvent by PhSH yields [FeCl3(SHPh)]. The kinetics of the second phase of the reaction with PhSH exhibits a non-linear dependence on the concentration of PhSH, analogous to the kinetics observed with PhS- and consistent with an associative mechanism. The cations [NHEt3]+, [NH2Et2]+ and [lutH]+ (lut = 2,6-dimethylpyridine) form ion pairs with [FeCl4]- which undergo substitution more rapidly than free [FeCl4]-.
Chemistry, School of Natural Sciences, University of Newcastle, Newcastle upon Tyne NE1 7RU, UK.
Brendan
B
Garrett
Richard A
RA
Henderson