2006/12/21 by Filipe Tiago de Oliveira, Arani Chanda, Deboshri Banerjee +6 · 3 citations
Chemistry · Medicine · Materials Science · #Metal-Catalyzed Oxygenation Mechanisms #Metal complexes synthesis and properties #Porphyrin and Phthalocyanine Chemistry
paper · doi:10.1126/science.1133417
openalex publication_date 2006/12/21 · openalex created_date 2016/06/24 · openalex updated_date 2026/08/01
Iron(V)-oxo species have been proposed as key reactive intermediates in the catalysis of oxygen-activating enzymes and synthetic catalysts. Here, we report the synthesis of [Fe(TAML)(O)]- in nearly quantitative yield, where TAML is a macrocyclic tetraamide ligand. Mass spectrometry, Mössbauer, electron paramagnetic resonance, and x-ray absorption spectroscopies, as well as reactivity studies and density functional theory calculations show that this long-lived (hours at -60 degrees C) intermediate is a spin S = 1/2 iron(V)-oxo complex. Iron-TAML systems have proven to be efficient catalysts in the decomposition of numerous pollutants by hydrogen peroxide, and the species we characterized is a likely reactive intermediate in these reactions.