Dioxygen activation and reduction by a soluble iron phthalocyanine

Iron ions in a square-planar coordination can bind molecules at the vacant axial positions and are able to transform them in stoichiometric and catalytic reactions. Nature takes advantage of these properties by incorporating iron into porphyrin systems, which play a key role not only in the binding...

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Main Authors: Iwanov, Christian (Author) , Hopp, Moritz Philipp (Author) , Lorenz, Domenik (Author) , Ballmann, Joachim (Author) , Enders, Markus (Author)
Format: Article (Journal)
Language:English
Published: 13 October 2023
In: Chemistry - a European journal
Year: 2023, Pages: 1-8
ISSN:1521-3765
DOI:10.1002/chem.202302761
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/chem.202302761
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202302761
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Author Notes:Christian Iwanov, Moritz Philipp Hopp, Domenik Lorenz, Joachim Ballmann, and Markus Enders
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Summary:Iron ions in a square-planar coordination can bind molecules at the vacant axial positions and are able to transform them in stoichiometric and catalytic reactions. Nature takes advantage of these properties by incorporating iron into porphyrin systems, which play a key role not only in the binding and transport of oxygen, but also in catalytic oxidation and reduction reactions involving cytochrome P450. Although these systems have been studied extensively, there are still unresolved questions regarding the interplay between the iron ions and the surrounding ligands. Phthalocyanines (Pc) create a similar environment for metal atoms and FePc is known for a long time. However, without axial ligands FePc aggregates leading to solids of low solubility. In this work we used a known six-coordinate iron phthalocyanine derivative with bulky substituents and removed the stabilizing axial ligands. The resulting paramagnetic, four-coordinate compound does not aggregate and dissolves well so that NMR spectroscopy can be employed for studying the molecular structure and the reactivity. Solvent molecules bind weakly to the iron centers and oxygen is reduced in the presence of H-atom donors. The stoichiometric and catalytic reactivity with oxygen was studied in more detail.
Item Description:Gesehen am 27.11.2023
Physical Description:Online Resource
ISSN:1521-3765
DOI:10.1002/chem.202302761