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Photochemistry of the [Fe4(mu3-S)3(NO)7]- complex in the presence of S-nucleophiles : a spectroscopic study

Photochemistry of the [Fe4(mu3-S)3(NO)7]- complex ...

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dc.contributor.author Chmura-Skirlińska, Antonina [SAP14006155] pl
dc.contributor.author Szaciłowski, Konrad [SAP11115985] pl
dc.contributor.author Waksmundzka-Góra, Anna pl
dc.contributor.author Stasicka, Zofia pl
dc.date.accessioned 2014-12-20T11:00:37Z
dc.date.available 2014-12-20T11:00:37Z
dc.date.issued 2006 pl
dc.identifier.issn 1089-8603 pl
dc.identifier.uri http://ruj.uj.edu.pl/xmlui/handle/item/2391
dc.language eng pl
dc.title Photochemistry of the [Fe4(mu3-S)3(NO)7]- complex in the presence of S-nucleophiles : a spectroscopic study pl
dc.type JournalArticle pl
dc.description.physical 247-260 pl
dc.abstract.en Biological systems usually contain cysteine, glutathione or other sulfur-containing biomolecules. These S-nucleophiles were found to affect drastically the [Fe(4)(mu(3)-S)(3)(NO)(7)](-) photolysis pathway generating products completely different from that of the neat cluster, which produces Fe(II) and NO and S(2-). The effect is interpreted in terms of formation of a pseudo-cubane adduct, [Fe(4)(mu(3)-S)(3)(mu(3)-SR)(NO)(7)](2-), whose existence in equilibrium with the parent complex has no detectable influence on the spectral properties, whereas shifts the redox potential and induces photoconversion leading to the Fe(III) species and N(2)O. Characteristic bond lengths, bond angles and atomic Mulliken charges were calculated using semi-empirical quantum chemical methods for the RBS anion and a series of pseudo-cubane complexes with S-donor or N-donor ligands. The results justify the hypothesis of the adduct formation and show that only in case of S-ligands the higher contribution of the Fe(III)-NO(-) components in adduct than in RBS is observed, which on excitation can undergo heterolytic cleavage yielding Fe(III) and NO(-), converted rapidly into N(2)O. These results are crucial in understanding the physiological activity of RBS. Fe(III) formation can be detected only when the S-ligand enables formation of a stable Fe(III) compound; the effect was recorded in the presence of sulfide, thioglycolate, 2-mercaptopropionate, mercaptosuccinate, penicillamine, 2,3-dimercaptosuccinate, 2,3-dimercaptopropanol, and thiocyanate. For all these S-ligands the Fe(III) photoproducts were identified and characterised. In the case of other thiolates, their excess results in fast reduction of Fe(III) to Fe(II), whereas N(2)O can be still detected. Quantum yields of Fe(III) formation in the presence of the S-ligands are considerably higher than that of the Fe(II) photoproduction from neat [Fe(4)(mu(3)-S)(3)(NO)(7)](-). pl
dc.description.volume 14 pl
dc.description.number 3 pl
dc.identifier.doi 10.1016/j.niox.2005.10.005 pl
dc.identifier.eissn 1089-8611 pl
dc.title.journal Nitric Oxide pl
dc.language.container eng pl
dc.affiliation Pion Rektora : Jagiellońskie Centrum Rozwoju Leków pl
dc.subtype Article pl


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