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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.
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.
URL: http://dx.doi.org/10.1080/00958971003671819
DOI: 10.1080/00958971003671819
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