Key result
Reaction of synthetic [2Fe-2S] and [4Fe-4S] clusters with nitric oxide or trityl-S-nitrosothiol results in the formation of dinitrosyl iron complexes, highlighting the role of thiolate-to-iron ratios.
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The study demonstrates chemical pathways for the reaction of iron-sulfur clusters with nitric oxide, highlighting the role of thiolate-to-iron ratios in stabilizing DNICs.
The interaction of nitric oxide (NO) with iron-sulfur cluster proteins results in degradation and breakdown of the cluster to generate dinitrosyl iron complexes (DNICs). In some cases the formation of DNICs from such cluster systems can lead to activation of a regulatory pathway or the loss of enzyme activity. In order to understand the basic chemistry underlying these processes, we have investigated the reactions of NO with synthetic [2Fe-2S] and [4Fe-4S] clusters. Reaction of excess NO(g) with solutions of [Fe2S2(SR)4](2-) (R = Ph, p-tolyl (4-MeC6H4), or 1/2 (CH2)2-o-C6H4) cleanly affords the respective DNIC, [Fe(NO)2(SR)2](-), with concomitant reductive elimination of the bridging sulfide ligands as elemental sulfur. The structure of (Et4N)[Fe(NO)2(S-p-tolyl)2] was verified by X-ray crystallography. Reactions of the [4Fe-4S] clusters, [Fe4S4(SR)4](2-) (R = Ph, CH2Ph, (t)Bu, or 1/2 (CH2)-m-C6H4) proceed in the absence of added thiolate to yield Roussin's black salt, [Fe4S3(NO)7](-). In contrast, (Et4N)2[Fe4S4(SPh)4] reacts with NO(g) in the presence of 4 equiv of (Et4N)(SPh) to yield the expected DNIC. For all reactions, we could reproduce the chemistry effected by NO(g) with the use of trityl-S-nitrosothiol (Ph3CSNO) as the nitric oxide source. These results demonstrate possible pathways for the reaction of iron-sulfur clusters with nitric oxide in biological systems and highlight the importance of thiolate-to-iron ratios in stabilizing DNICs.
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Harrop et al. (2008) studied this question. Nitric oxide and nitrosothiols was evaluated on Formation of dinitrosyl iron complexes (DNICs). Reaction of synthetic [2Fe-2S] and [4Fe-4S] clusters with nitric oxide or trityl-S-nitrosothiol results in the formation of dinitrosyl iron complexes, highlighting the role of thiolate-to-iron ratios.
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