Nitrosyls iron-sulfur clusters

The interactions of NO with the iron-sulfur cluster moieties of several enzymes generate iron-sulfur-nitrosyl cluster compounds [156]. However, synthetic nitrosyl clusters such as Roussins black salt (RBS), Roussins red salt (RRS), Roussins red ester (RRE) and [FeNOS]4 (Fig. 5.3) are well known [129, 157] and can be synthesized easily [158-164]. For example, the RBS can be prepared by mixing FeS04 with NaN03 and (NH4)2S in aqueous solution [158]. RRE salts are generally insoluble in water, but recently the water soluble sulfonated derivative, Na2[Fe2(SCH2CH2S03)2(N0)4], has been prepared [165]. 

Fig. 5.3 Structures of some well-known iron-sulfur cluster nitrosyls.

It is instructive, in this context, to compare the case of assembly of both nitrosylated iron sulfur tetranuclear clusters and the related clusters with pendant thiolate groups (13), with the laborious and stepwise initial synthesis (38) of cubane C8H8 this comparison is, of course, simply one between thermodynamically controlled processes, in the case of the iron sulfur systems, and kinetically controlled reactions for C8H8 synthesis. 

The central role of the complexes [Fe(NO)2(SR)2]- in the reaction chemistry of iron-sulfur-nitrosyl complexes and their very ready formation both in in vitro and in vivo (108,123-125,128,129) suggest that the antimicrobial activity of nitrite depends not only upon the disruption of respiration [by destruction of the natural iron-sulfur clusters of redox proteins (70S)] but also specifically upon the formation... 

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