15446-31-8Relevant articles and documents
A tetranitrosyl [4Fe-4S] cluster forms en route to roussins black anion: Nitric oxide reactivity of [Fe4S4(LS3)L] 2-
Victor, Eric,Lippard, Stephen J.
, p. 5311 - 5320 (2014)
Previous studies provide evidence that [4Fe-4S] clusters serve as targets of reactive nitrogen oxide species in biology. The products of this reaction range from dinitrosyliron complexes, [Fe(NO)2L2] -, to Roussins black anion, [Fe4S3(NO) 7]-. To date, the pathways by which these reactions occur have not been fully elucidated. In this study, we prepared the site-differentiated complexes [Fe4S4(LS 3)L]2- (LS3 = 1,3,5-tris(4,6-dimethyl-3- mercaptophenylthio)-2,4,6-tris(p-tolylthio)benzene; L = Cl, SEt, SPh, N 3, 2-SPyr, Tp, S2CNEt2) to serve as synthetic models for biological [4Fe-4S] clusters and studied their reactivity toward NO(g) and Ph3CSNO. The products were characterized by X-ray crystallography, mass spectrometry, and IR, electron paramagnetic resonance (EPR), and 1H NMR spectroscopy. In all cases reported here, the reactions proceed via formation of the S = 1/2 species [Fe4S4(NO)4]-, which ultimately converts to EPR-silent [Fe4S3(NO)7] -.
Iron(II/III) Halide Complexes Promote the Interconversion of Nitric Oxide and S-Nitrosothiols through Reversible Fe-S Interaction
Poptic, Anna L.,Zhang, Shiyu
supporting information, p. 5190 - 5197 (2021/04/06)
Heme and non-heme iron in biology mediate the storage/release of NO? from S-nitrosothiols as a means to control the biological concentration of NO?. Despite their importance in many physiological processes, the mechanisms of N-S bond formation/cleavage at Fe centers have been controversial. Herein, we report the interconversion of NO? and S-nitrosothiols mediated by FeII/FeIII chloride complexes. The reaction of 2 equiv of S-nitrosothiol (Ph3CSNO) with [Cl6FeII2]2- results in facile release of NO? and formation of iron(III) halothiolate. Detailed spectroscopic studies, including in situ UV-vis, IR, and M?ssbauer spectroscopy, support the interaction of the S atom with the FeII center. This is in contrast to the proposed mechanism of NO? release from the well-studied red product κ1-N bound S-nitrosothiol FeII complex, [(CN)5Fe(κ1-N-RSNO)]3-. Additionally, FeIII chloride can mediate NO? storage through the formation of S-nitrosothiols. Treatment of iron(III) halothiolate with 2 equiv of NO? regenerates Ph3CSNO with the FeII source trapped as the S = 3/2 {FeNO}7 species [Cl3FeNO]-, which is inert toward further coordination and activation of S-nitrosothiols. Our work demonstrates how labile iron can mediate the interconversion of NO?/thiolate and S-nitrosothiol, which has important implications toward how Nature manages the biological concentration of free NO?.
Imidazole Promoted Highly Efficient Large-Scale Thiol-Free Synthesis of Symmetrical Disulfides in Aqueous Media
Mokhtari, Babak,Kiasat, Ali Reza,Monjezi, Javid
, p. 1573 - 1579 (2015/09/15)
A highly efficient and environmentally friendly method for the imidazole promoted preparation of symmetrical organic disulfides from Bunte salts is described. This thiol-free procedure produces the desired disulfides even on a large scale by reaction of Bunte salts with imidazole in good to high yields in aqueous media.
