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Kinetics and mechanism of the reactions of [FeCl4]- with PhS or PhSH in MeCN, and the role of cations containing N-H groups

Lookup NU author(s): Brendan Garrett, Professor Richard Henderson


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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 [FeCl 4(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 [FeCl 3(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]+, [NH2Et 2]+ and [lutH]+ (lut = 2, 6-dimethylpyridine) form ion pairs with [FeCl4]- which undergo substitution more rapidly than free [FeCl4]-. © The Royal Society of Chemistry 2005.

Publication metadata

Author(s): Garrett B, Henderson RA

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2005

Issue: 14

Pages: 2395-2402

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry


DOI: 10.1039/b503501e


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