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Binding Nucleophiles to [Fe4Y4Cl4]2- (Y = S or Se) can Increase or Suppress the Rate of Proton Transfer to the Cluster

Lookup NU author(s): Katie Bates, Professor Richard Henderson


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In the proton transfer reactions between [Fe4Y 4Cl4]2- (Y = S or Se) and [pyrH]+ (pyr = pyrrolidine) in the presence of a variety of nucleophiles (L = I -, Br-, PhS-, EtS- or ButNC), initial binding of the nucleophile can occur to generate [Fe4Y 4Cl4(L)]n-. The subsequent rate of proton transfer depends markedly on the nature of L. Stopped-flow kinetic studies show that proton transfer from [pyrH]+ to [Fe4Y 4Cl4]2- {Sk4, = (2.1 ± 0.5) × 104 dm3 mol-1 s -1; Sek4 = (8.0 ± 0.5) × 10 3 dm3 mol-1 s-1} is increased by prior binding of L = PhS- or ButNC to form [Fe 4Y4Cl4(L)]n-(Sk 7L ∼ 1 × 106 dm3 mol -1 s-1), but prior binding of L = I-, Br -, or EtS- to the clusters inhibits the rate of proton transfer {e.g. Sk7I = (6.0 ± 0.8) × 102 dm3 mol-1 s-1; Sek7I = (4.5 ± 0.5) × 10 2 dm3 mol-1 s-1}. This behavior is correlated with the bonding characteristics of L and the effect this has on bond length reorganization within the cluster upon proton transfer. © 2008 American Chemical Society.

Publication metadata

Author(s): Bates K, Henderson RA

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2008

Volume: 47

Issue: 13

Pages: 5850-5858

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society


DOI: 10.1021/ic800142e

PubMed id: 18540596


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