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Kinetics and mechanism of the acid-catalyzed substitution reactions of [Fe6S9(SEt)(2)]4-

Lookup NU author(s): Adrain John Dunford, Professor Richard Henderson


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Kinetic studies on the reaction between [Fe6S9(SEt)(2)](4-) and PhS- in the presence of [NHEt3](+) to form [Fe6S9(SPh)(2)](4-) are consistent with an acid-catalyzed dissociative mechanism involving rapid protonation of the cluster at both an ethanethiolate and mu(n)-S, followed by rate-limiting dissociation of the coordinated ethanethiol, and finally rapid attack of PhSH at the vacant site to form the product. Analysis of the kinetic data gives the pK(a) of [Fe6S9(SEt)(2)](4-) as 17.9, in line with other synthetic Fe-S-based clusters and consistent with protonation of a mu(n)-S in the cluster core. Further kinetic studies have indicated that Cl-, CN-, (BuNC)-N-t, or imidazole can bind and influence the lability of the cluster.

Publication metadata

Author(s): Dunford AJ, Henderson RA

Publication type: Article

Publication status: Published

Journal: Journal of Coordination Chemistry

Year: 2010

Volume: 63

Issue: 14-16

Pages: 2507-2516

Print publication date: 03/03/2010

ISSN (print): 0095-8972

ISSN (electronic): 1026-7441

Publisher: Taylor & Francis Ltd.


DOI: 10.1080/00958971003671819


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