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The present work provides theoretical and experimental foundations for the ability of dinitrosyl iron complexes (DNICs) with thiol-containing ligands to be not only the donors of neutral NO molecules, but also the donors of nitrosonium cations (NO(+)) in living organisms ensuring S-nitrosation of various proteins and low-molecular-weight compounds. It is proposed that the emergence of those cations in DNICs is related to disproportionation reaction of NO molecules, initiated by their binding with Fe(2+) ions (two NO molecules per one ion). At the same time, possible hydrolysis of iron-bound nitrosonium cations is prevented by the electron density transition to nitrosonium cations from sulfur atoms of thiol-containing ligands, which are included in the coordination sphere of iron. It allows supposing that iron in iron–nitrosyl complexes of DNICs has a d(7) electronic configuration. This supposition is underpinned by experimental data revealing that a half of nitrosyl ligands are converted into S-nitrosothiols (RSNOs) when those complexes decompose, with the other half of those ligands released in the form of neutral NO molecules.
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10.1007/s00723-020-01270-6
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document_parses/pdf_json/fd9d27b3e79979ccb5fe29c97a845929b230e50d.json
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document_parses/pmc_json/PMC7572240.xml.json
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How is Nitric Oxide (NO) Converted into Nitrosonium Cations (NO(+)) in Living Organisms? (Based on the Results of Optical and EPR Analyses of Dinitrosyl Iron Complexes with Thiol-Containing Ligands)
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