Chemical and spectroscopic evidence for an FeV-oxo complex |
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Authors: | Tiago de Oliveira Filipe Chanda Arani Banerjee Deboshri Shan Xiaopeng Mondal Sujit Que Lawrence Bominaar Emile L Münck Eckard Collins Terrence J |
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Affiliation: | Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA. |
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Abstract: | 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, M?ssbauer, 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. |
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