61003-16-5

Upstream product

• 10102-43-9 nitrogen(II) oxide 
• 21050-13-5 bis(triphenylphosphine)iminium chloride 
• 6493-73-8 dibenzyltrisulfide 
• 10545-99-0 sulfur dichloride 
• 68-12-2 N,N-dimethyl-formamide 

Relevant academic research and scientific papers

Iron(II/III) Halide Complexes Promote the Interconversion of Nitric Oxide and S-Nitrosothiols through Reversible Fe-S Interaction

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?.

Synthesis and characterization of new heterometallic iron sulfur nitrosyl clusters

The reactivity of the (PPN)2[Fe8S6(NO)8] and (PPN)2[Fe6S6(NO)6] clusters is explored and new derivative clusters have been synthesized and structurally characterized. The unique (PPN)2Fe4S4(NO)6 "open-cubane" cluster with a chair like Fe4S4 core is obtained along with the mixed metal pentandite-like clusters (PPN)2[Mo2Fe6S6(NO)6(CO)6], (PPr3)2Cu2Fe6S6(NO)6, (PPr3)4Cu4Fe4S6(NO)4, (PPr3)2Ni2Fe6S6(NO)6, (PPr3)3Ni3Fe4S6(NO)4. The rich electrochemistry of the mixed metal clusters is presented as well.

{FeNO}7-Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

Mononitrosyl–iron compounds (MNICs) of the Enemark–Feltham {FeNO}7 type can be divided into a doublet (S=1/2) and a quartet (S=3/2) spin variant. The latter relies on weak-field co-ligands such as amine carboxylates. Aqua-only co-ligation appears to exist in the long-known “brown-ring” [Fe(H2O)5(NO)]2+ cation, which was prepared originally from ferrous salts and NO in sulfuric acid. A chloride variant of this species, the green [FeCl3(NO)]? ion, was first prepared analoguosly by using hydrochloric instead of sulfuric acid. As a tetrahedral species, it is the simple prototype of sulfur-bonded {FeNO}7 (S=3/2) MNICs of biological significance. Although it has been investigated for more than a century, neither clean preparative routes nor reliable structural parameters were available for the [FeCl3(NO)]? ion and related species such as the [FeCl2(NO)2]? ion, a prototypical dinitrosyliron species (a “DNIC”). In this work, both issues have been resolved. In addition, we report on a computational study on the ground- and excited-state properties including an assignment of the chromophoric transitions. Photoinduced metastable isomers were characterised in a combined experimental and computational approach that resulted in the confirmation of a single photoinduced linkage isomer of the paramagnetic nitrosyl–metal coordination entity.