Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds
The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([FeIII(TEPyP)]5+), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([FeIII(TPPS)]3-), and microperoxidase 11 ([FeIII(MP11)])...
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todo:paper_01620134_v104_n1_p30_Bari2023-10-03T15:01:27Z Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds Bari, S.E. Amorebieta, V.T. Gutiérrez, M.M. Olabe, J.A. Doctorovich, F. Catalysis Hydroxylamine Iron(III) microperoxidase 11 Iron(III) porphyrinates Nitrogen metabolism ammonia ferric ion ferrous ion free radical hydroxylamine iron nitrogen nitrous oxide peroxidase porphyrin derivative anaerobic metabolism article catalysis chemical reaction controlled study kinetics oxidation reduction potential pH Catalysis Hydroxylamine Metalloporphyrins Nitric Oxide Peroxidases Pyridines Solubility Water The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([FeIII(TEPyP)]5+), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([FeIII(TPPS)]3-), and microperoxidase 11 ([FeIII(MP11)]) were studied for different [FeIII(Porph)]/[HA] ratios, under anaerobic conditions at neutral pH. Efficient catalytic processes leading to the disproportionation of HA by these iron(III) porphyrinates were evidenced for the first time. As a common feature, only N2 and N2O were found as gaseous, nitrogen-containing oxidation products, while NH3 was the unique reduced species detected. Different N2/N2O ratios obtained with these three porphyrinates strongly suggest distinctive mechanistic scenarios: while [FeIII(TEPyP)]5+ and [FeIII(MP11)] formed unknown steady-state porphyrinic intermediates in the presence of HA, [FeIII(TPPS)]3- led to the well characterized soluble intermediate, [FeII(TPPS)NO]4-. Free-radical formation was only evidenced for [FeIII(TEPyP)]5+, as a consequence of a metal centered reduction. We discuss the catalytic pathways of HA disproportionation on the basis of the distribution of gaseous products, free radicals formation, the nature of porphyrinic intermediates, the FeII/FeIII redox potential, the coordinating capabilities of each complex, and the kinetic analysis. The absence of NO2- revealed either that no HAO-like activity was operative under our reaction conditions, or that NO2-, if formed, was consumed in the reaction milieu. © 2009 Elsevier Inc. All rights reserved. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_01620134_v104_n1_p30_Bari |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Catalysis Hydroxylamine Iron(III) microperoxidase 11 Iron(III) porphyrinates Nitrogen metabolism ammonia ferric ion ferrous ion free radical hydroxylamine iron nitrogen nitrous oxide peroxidase porphyrin derivative anaerobic metabolism article catalysis chemical reaction controlled study kinetics oxidation reduction potential pH Catalysis Hydroxylamine Metalloporphyrins Nitric Oxide Peroxidases Pyridines Solubility Water |
| spellingShingle |
Catalysis Hydroxylamine Iron(III) microperoxidase 11 Iron(III) porphyrinates Nitrogen metabolism ammonia ferric ion ferrous ion free radical hydroxylamine iron nitrogen nitrous oxide peroxidase porphyrin derivative anaerobic metabolism article catalysis chemical reaction controlled study kinetics oxidation reduction potential pH Catalysis Hydroxylamine Metalloporphyrins Nitric Oxide Peroxidases Pyridines Solubility Water Bari, S.E. Amorebieta, V.T. Gutiérrez, M.M. Olabe, J.A. Doctorovich, F. Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds |
| topic_facet |
Catalysis Hydroxylamine Iron(III) microperoxidase 11 Iron(III) porphyrinates Nitrogen metabolism ammonia ferric ion ferrous ion free radical hydroxylamine iron nitrogen nitrous oxide peroxidase porphyrin derivative anaerobic metabolism article catalysis chemical reaction controlled study kinetics oxidation reduction potential pH Catalysis Hydroxylamine Metalloporphyrins Nitric Oxide Peroxidases Pyridines Solubility Water |
| description |
The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([FeIII(TEPyP)]5+), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([FeIII(TPPS)]3-), and microperoxidase 11 ([FeIII(MP11)]) were studied for different [FeIII(Porph)]/[HA] ratios, under anaerobic conditions at neutral pH. Efficient catalytic processes leading to the disproportionation of HA by these iron(III) porphyrinates were evidenced for the first time. As a common feature, only N2 and N2O were found as gaseous, nitrogen-containing oxidation products, while NH3 was the unique reduced species detected. Different N2/N2O ratios obtained with these three porphyrinates strongly suggest distinctive mechanistic scenarios: while [FeIII(TEPyP)]5+ and [FeIII(MP11)] formed unknown steady-state porphyrinic intermediates in the presence of HA, [FeIII(TPPS)]3- led to the well characterized soluble intermediate, [FeII(TPPS)NO]4-. Free-radical formation was only evidenced for [FeIII(TEPyP)]5+, as a consequence of a metal centered reduction. We discuss the catalytic pathways of HA disproportionation on the basis of the distribution of gaseous products, free radicals formation, the nature of porphyrinic intermediates, the FeII/FeIII redox potential, the coordinating capabilities of each complex, and the kinetic analysis. The absence of NO2- revealed either that no HAO-like activity was operative under our reaction conditions, or that NO2-, if formed, was consumed in the reaction milieu. © 2009 Elsevier Inc. All rights reserved. |
| format |
JOUR |
| author |
Bari, S.E. Amorebieta, V.T. Gutiérrez, M.M. Olabe, J.A. Doctorovich, F. |
| author_facet |
Bari, S.E. Amorebieta, V.T. Gutiérrez, M.M. Olabe, J.A. Doctorovich, F. |
| author_sort |
Bari, S.E. |
| title |
Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds |
| title_short |
Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds |
| title_full |
Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds |
| title_fullStr |
Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds |
| title_full_unstemmed |
Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds |
| title_sort |
disproportionation of hydroxylamine by water-soluble iron(iii) porphyrinate compounds |
| url |
http://hdl.handle.net/20.500.12110/paper_01620134_v104_n1_p30_Bari |
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