Base-controlled mechanistic divergence between iron(iv )-oxo and iron(iii )-hydroperoxo in the H2O2 activation by a nonheme iron(ii ) complex
| Autor: | Antoine Bohn, Katell Sénéchal-David, Christian Herrero, Régis Guillot, Clémence Chinaux-Chaix, Frédéric Banse, Jean-Noël Rebilly, Khaled Cheaib |
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| Přispěvatelé: | Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Chemistry Ligand Radical Reaction intermediate [CHIM.INOR]Chemical Sciences/Inorganic chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Heterolysis Peroxide 0104 chemical sciences Homolysis Inorganic Chemistry chemistry.chemical_compound Oxidizing agent [CHIM]Chemical Sciences Hydrogen peroxide ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Dalton Transactions Dalton Transactions, Royal Society of Chemistry, 2019, 48 (45), pp.17045-17051. ⟨10.1039/C9DT03487K⟩ |
| ISSN: | 1477-9234 1477-9226 |
| Popis: | Activation of hydrogen peroxide by FeII salts (Fenton systems) leads to a myriad of oxidizing agents whose nature, FeIVO, or hydroxyl radicals and FeIII species, is dictated by the reaction conditions, in particular the pH value. Using the non heme FeII complex [FeII(L52)(CH3CN)]2+ (1) (where L52 is the pentadentate ligand N-methyl-N,N′,N′-tris(2-pyridylmethyl)ethane-1,2-diamine) we have observed the simultaneous formation of two reaction intermediates, [FeIV(O)(L52)]2+ and [FeIII(OOH)(L52)]2+, in its reaction with excess hydrogen peroxide in the presence of sub-stoichiometric amounts of triethylamine. Kinetic and spectroscopic monitoring of the reaction mixture and of independently prepared [FeIV(O)(L52)]2+ in the presence of the different constituents of the reaction mixture allows drawing a mechanistic scheme. These two reactive species are formed simultaneously following two independent and competitive pathways. [FeIV(O)(L52)]2+ is obtained via heterolytic O–O cleavage of the oxidant assisted by the base in a peroxidase-like mechanism whereas [FeIII(OOH)(L52)]2+ is generated upon homolytic O–O cleavage of hydrogen peroxide. The relative contribution of these two pathways can be tuned by adjusting the amount of base used. |
| Databáze: | OpenAIRE |
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