Reactivities of iron(IV)-oxido compounds with pentadentate bispidine ligands
The FeIV--O complexes of bispidines (3,7-diazabicyclo[3.3.1]nonane derivatives) are known to be highly reactive oxidants - with the tetradentate bispidine, the so far most reactive ferryl complex has been reported and two isomeric pentadentate ligands also lead to very reactive high-valent oxidants....
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| Main Authors: | , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
April 2023
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| In: |
Journal of inorganic biochemistry
Year: 2023, Volume: 241, Pages: 1-10 |
| ISSN: | 1873-3344 |
| DOI: | 10.1016/j.jinorgbio.2023.112123 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1016/j.jinorgbio.2023.112123 Verlag, lizenzpflichtig, Volltext: https://linkinghub.elsevier.com/retrieve/pii/S0162013423000053 |
| Author Notes: | Katharina Bleher, Peter Comba, Dustin Kass, Kallol Ray, Hubert Wadepohl |
| Summary: | The FeIV--O complexes of bispidines (3,7-diazabicyclo[3.3.1]nonane derivatives) are known to be highly reactive oxidants - with the tetradentate bispidine, the so far most reactive ferryl complex has been reported and two isomeric pentadentate ligands also lead to very reactive high-valent oxidants. With a series of 4 new bispidine derivatives we now try to address the question why the bispidine scaffold in general leads to very reactive oxidants and how this can be tuned by ligand modifications. The study is based on a full structural, spectroscopic and electrochemical analysis of the iron(II) precursors, spectroscopic data of the iron(IV)-oxido complexes, a kinetic analysis of the stoichiometric oxidation of thioanisole by five different bispidine-iron(IV)-oxido complexes and on product analyses of reactions by the five ferryl oxidants with thioanisole, beta-methylstyrene and cisstilbene as substrates. |
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| Item Description: | Gesehen am 24.03.2023 |
| Physical Description: | Online Resource |
| ISSN: | 1873-3344 |
| DOI: | 10.1016/j.jinorgbio.2023.112123 |