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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.
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
URL: http://dx.doi.org/10.1021/ic800142e
DOI: 10.1021/ic800142e
PubMed id: 18540596
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