Water-Soluble Nitroxyl Porphyrin Complexes FeIITPPSHNO and FeIITPPSNO- Obtained from Isolated FeIITPPSNO·
The first biomimetic water soluble FeII-porphyrin nitroxyl complexes were obtained and characterized by UV-Vis in protonated and deprotonated forms by reduction of previously isolated and characterized FeIITPPSNO?. The pKa involved in the FeII-HNO ⇄ FeII-NO− + H+ equilibrium was estimated to be arou...
| Autores: | , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2019 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/121799 |
| Acceso en línea: | http://hdl.handle.net/11336/121799 |
| Access Level: | acceso abierto |
| Palabra clave: | IRON PORPHYRIN NITROXYL HNO https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | The first biomimetic water soluble FeII-porphyrin nitroxyl complexes were obtained and characterized by UV-Vis in protonated and deprotonated forms by reduction of previously isolated and characterized FeIITPPSNO?. The pKa involved in the FeII-HNO ⇄ FeII-NO− + H+ equilibrium was estimated to be around 9.7. The FeIITPPSHNO complex spontaneously reoxidizes to the nitrosyl form following a first order kinetic decay with a measured kinetic constant of k = 0.017 s-1. Experiments show that the HNO adduct undergoes unimolecular homolytic cleavage of the H-NO bond. DFT calculations suggest a phlorin radical intermediate for this reaction. The deprotonated NO− complex resulted more stable, with a half-life of about 10 minutes. |
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