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• W2326476509 endingPage "11877" @default.
• W2326476509 startingPage "11874" @default.
• W2326476509 abstract "The crosstalk between two biologically important signaling molecules, nitric oxide (NO) and hydrogen sulfide (H2S), proceeds via elusive mechanism(s). Herein we report the formation of H2S by the action of NO on synthetic [2Fe-2S] clusters when the reaction environment is capable of providing a formal H• (e–/H+). Nitrosylation of (NEt4)2[Fe2S2(SPh)4] (1) in the presence of PhSH or tBu3PhOH results in the formation of (NEt4)[Fe(NO)2(SPh)2] (2) and H2S with the concomitant generation of PhSSPh or tBu3PhO•. The amount of H2S generated is dependent on the electronic environment of the [2Fe-2S] cluster as well as the type of H• donor. Employment of clusters with electron-donating groups or H• donors from thiols leads to a larger amount of H2S evolution. The 1/NO reaction in the presence of PhSH exhibits biphasic decay kinetics with no deuterium kinetic isotope effect upon PhSD substitution. However, the rates of decay increase significantly with the use of 4-MeO-PhSH or 4-Me-PhSH in place of PhSH. These results provide the first chemical evidence to suggest that [Fe-S] clusters are likely to be a site for the crosstalk between NO and H2S in biology." @default.
• W2326476509 created "2016-06-24" @default.
• W2326476509 creator A5014930185 @default.
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• W2326476509 date "2014-08-18" @default.
• W2326476509 modified "2023-09-30" @default.
• W2326476509 title "Nitric Oxide Reactivity of [2Fe-2S] Clusters Leading to H₂S Generation" @default.
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• W2326476509 doi "https://doi.org/10.1021/ja505415c" @default.
• W2326476509 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/25113815" @default.
• W2326476509 hasPublicationYear "2014" @default.
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