106709-47-1Relevant academic research and scientific papers
Generation of H2S from Thiol-Dependent NO Reactivity of Model [4Fe-4S] Cluster and Roussin's Black Anion
Oakley, Kady M.,Zhao, Ziyi,Lehane, Ryan L.,Ma, Ji,Kim, Eunsuk
, p. 15910 - 15917 (2021)
Iron-sulfur clusters (Fe-S) have been well established as a target for nitric oxide (NO) in biological systems. Complementary to protein-bound studies, synthetic models have provided a platform to study what iron nitrosylated products and byproducts are produced depending on a controlled reaction environment. We have previously shown a model [2Fe-2S] system that produced a dinitrosyl iron complex (DNIC) upon nitrosylation along with hydrogen sulfide (H2S), another important gasotransmitter, in the presence of thiol, and hypothesized a similar reactivity pattern with [4Fe-4S] clusters which have largely produced inconsistent reaction products across biological and synthetic systems. Roussin's black anion (RBA), [Fe4(μ3-S)3(NO)7]-, is a previously established reaction product from synthetic [4Fe-4S] clusters with NO. Here, we present a new reactivity for the nitrosylation of a synthetic [4Fe-4S] cluster in the presence of thiol and thiolate. [Et4N]2[Fe4S4(SPh)4] (1) was nitrosylated in the presence of excess PhSH to generate H2S and an "RBA-like"intermediate that when further reacted with [NEt4][SPh] produced a {Fe(NO)2}9 DNIC, [Et4N][Fe(NO)2(SPh)2] (2). This "RBA-like"intermediate proved difficult to isolate but shares striking similarities to RBA in the presence of thiol based on IR υ(NO) stretching frequencies. Surprisingly, the same reaction products were produced when the reaction started with RBA and thiol. Similar to 1/NO, RBA in the presence of thiol and thiolate generates stoichiometric amounts of DNIC while releasing its bridging sulfides as H2S. These results suggest not only that RBA may not be the final product of [4Fe-4S] + NO but also that RBA has unprecedented reactivity with thiols and thiolates which may explain current challenges around identifying biological nitrosylated Fe-S clusters.
Nitric oxide reactivity of [2Fe-2S] clusters leading to H2S generation
Tran, Camly T.,Williard, Paul G.,Kim, Eunsuk
supporting information, p. 11874 - 11877 (2014/12/10)
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[Fe2S 2(SPh)4] (1) in the presence of PhSH or tBu3PhOH results in the formation of (NEt 4)[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 H 2S 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.
Reactions of synthetic [2Fe-2S] and [4Fe-4S] clusters with nitric oxide and nitrosothiols
Harrop, Todd C.,Tonzetich, Zachary J.,Reisner, Erwin,Lippard, Stephen J.
, p. 15602 - 15610 (2009/03/12)
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
Synthesis and Structure of (-), the Monomer of Roussin's Phenyl Ester
Strasdeit, Henry,Krebs, Bernt,Henkel, Gerald
, p. 1357 - 1362 (2007/10/02)
The complex (Et4N) (2) has been obtained as black crystals by treatment of K*H2O with potassium hydroxide in molten diphenyldisulfide and subsequent addition of methanol and tetraethylammonium chloride. (2) is orthorhombic, space group Pbca, Z = 8, with a = 18.853(3), b = 17.958(3), and c = 13.283(2) Angstroem at 140 K.The X-ray structure of 2 has been refined to R1 (R2) = 2.7percent (3.1percent).It reveals a pseudotetrahedral S2N2 arrangement around the iron atom (Fe-S 2.280, Fe-N 1.679 Angstroem (mean values), S-Fe-S 109.73(2) deg, N-Fe-N 117.36(9) deg) and Fe-N-O groups of the linear type (N-O 1.180 Angstroem, Fe-N-O 169.0 deg (mean values)).The N-O bond order is 2.2.Structural properties as well as the low Moessbauer isomeric shift (+0.08 mm/s relative to Fe metal) are indicative of strong Fe-N ?-back bonding and a major contribution of the mesomeric form . - Keywords: Iron-Nitrosyl Thiolates, Synthesis, X-Ray, Roussin's Phenyl Ester
