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Abstract:

Sodium nitroprusside (SNP, Na 2 [Fe(CN) 5 (NO)] •2H 2 O) is a widely used NO-donor hypotensive agent, containing the formally described nitrosonium (NO + ) ligand, which may be redox-interconverted to the corresponding one-electron (NO) and two-electron (NO - /HNO) reduced bound species. Thus, the chemistry of the three nitrosyl ligands may be explored with adequate, biologically relevant substrates. The nitrosonium complex, [Fe(CN) 5 (NO)] 2- , is formed through a reductive nitrosylation reaction of [Fe III (CN) 5 (H 2 O)] 2- with NO, or, alternatively, through the coordination of NO 2 - to [Fe II (CN) 5 (H 2 O)] 3- and further proton-assisted dehydration. It is extremely inert toward NO + -dissociation, and behaves as an electrophile toward different bases: OH - , amines, thiolates, etc. Also, SNP releases NO upon UV-vis photo-activation, with formation of [Fe III (CN) 5 (H 2 O)] 2- . The more electron rich [Fe(CN) 5 (NO)] 3- may be prepared from [Fe II (CN) 5 (H 2 O)] 3- and NO, and is also highly inert toward the dissociation of NO (k = 1.6 × 10 -5 s -1 , 25.0 °C, pH 10.2). It reacts with O 2 leading to SNP, with the intermediacy of a peroxynitrite adduct. The [Fe(CN) 5 (NO)] 3- ion is labile toward the release of trans-cyanide, forming the [Fe(CN) 4 (NO)] 2- ion. Both complexes exist in a pH-dependent equilibrium, and decompose thermally in the hours time scale, releasing cyanides and NO. The latter may further bind to [Fe(CN) 4 (NO)] 2- with formation of a singlet dinitrosyl species, [Fe(CN) 4 (NO) 2 ] 2- , which in turn is unstable toward disproportionation into SNP and N 2 O, and toward the parallel formation of a tetrahedral paramagnetic dinitrosyl compound, [Fe(CN) 2 (NO) 2 ]. Emerging studies with the putative nitroxyl complex, [Fe(CN) 5 (HNO)] 3- , should allow for a complete picture of the three nitrosyl ligands in the same pentacyano fragment. The present Perspective, based on an adequate characterization of structural and spectroscopic properties, will focus on the kinetic and mechanistic description of the above mentioned reactions, which display a versatile scenario, fundamentally related to the biologically relevant processes associated with NO reactivity. © 2008 The Royal Society of Chemistry.

Registro:

Documento: Artículo
Título:The coordination chemistry of nitrosyl in cyanoferrates. An exhibit of bioinorganic relevant reactions
Autor:Olabe, J.A.
Filiación:Department of Inorganic, Analytical and Physical Chemistry, INQUIMAE, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina
Palabras clave:Sodium; Coordination chemistry; Cyanoferrates; Relevant reactions; Sodium nitroprusside (SNP); Coordination reactions; antihypertensive agent; ligand; nitrogen oxide; nitroprusside sodium; animal; article; chemistry; inorganic chemistry; oxidation reduction reaction; Animals; Antihypertensive Agents; Chemistry, Bioinorganic; Ligands; Nitrogen Oxides; Nitroprusside; Oxidation-Reduction
Año:2008
Número:28
Página de inicio:3633
Página de fin:3648
DOI: http://dx.doi.org/10.1039/b803153c
Título revista:Dalton Transactions
Título revista abreviado:Dalton Trans.
ISSN:14779226
CAS:nitrogen oxide, 11104-93-1; nitroprusside sodium, 14402-89-2, 15078-28-1; Antihypertensive Agents; Ligands; Nitrogen Oxides; Nitroprusside, 15078-28-1
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v_n28_p3633_Olabe

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Citas:

---------- APA ----------
(2008) . The coordination chemistry of nitrosyl in cyanoferrates. An exhibit of bioinorganic relevant reactions. Dalton Transactions(28), 3633-3648.
http://dx.doi.org/10.1039/b803153c
---------- CHICAGO ----------
Olabe, J.A. "The coordination chemistry of nitrosyl in cyanoferrates. An exhibit of bioinorganic relevant reactions" . Dalton Transactions, no. 28 (2008) : 3633-3648.
http://dx.doi.org/10.1039/b803153c
---------- MLA ----------
Olabe, J.A. "The coordination chemistry of nitrosyl in cyanoferrates. An exhibit of bioinorganic relevant reactions" . Dalton Transactions, no. 28, 2008, pp. 3633-3648.
http://dx.doi.org/10.1039/b803153c
---------- VANCOUVER ----------
Olabe, J.A. The coordination chemistry of nitrosyl in cyanoferrates. An exhibit of bioinorganic relevant reactions. Dalton Trans. 2008(28):3633-3648.
http://dx.doi.org/10.1039/b803153c