INQUIMAE 12526
INSTITUTO DE QUIMICA, FISICA DE LOS MATERIALES, MEDIOAMBIENTE Y ENERGIA
Unidad Ejecutora - UE
artículos
Título:
Water-Soluble Nitroxyl Porphyrin Complexes Fe II TPPSHNO and Fe II TPPSNO – Obtained from Isolated Fe II TPPSNO •
Autor/es:
PELLEGRINO, JUAN; PELLEGRINO, JUAN; DOCTOROVICH, FABIO; DOCTOROVICH, FABIO; MAZZEO, AGOSTINA; MAZZEO, AGOSTINA
Revista:
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Editorial:
AMER CHEMICAL SOC
Referencias:
Año: 2019 vol. 141 p. 18521 - 18530
ISSN:
0002-7863
Resumen:
The first biomimetic water-soluble FeII-porphyrinnitroxyl complexes were obtained and characterized byUV−vis in protonated and deprotonated forms by reductionof previously isolated and characterized FeIITPPSNO?. ThepKa involved in the FeII−HNO ⇄ FeII−NO− + H+equilibrium was estimated to be around 9.7. TheFeIITPPSHNO complex spontaneously reoxidizes to thenitrosyl form following a first-order kinetic decay with ameasured kinetic constant of k = 0.017 s−1. Experiments showthat the HNO adduct undergoes unimolecular homolyticcleavage of the H−NO bond. DFT calculations suggest aphlorin radical intermediate for this reaction. The deprotonatedNO− complex resulted to be more stable, with a half-lifeof about 10 min.
