From the Iron Pentacarbonyl Cation to Heteroleptic η6-arene Carbonyls and bis-η6-arene Cations
© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH..
Partial ligand substitution at the iron pentacarbonyl radical cation generates novel half-sandwich complexes of the type [Fe(η6-arene)(CO)2]⋅+ (arene=1,3,5-tri-tert-butylbenzene, 1,3,5-trimethylbenzene, benzene and fluorobenzene). Of those, the bulkier 1,3,5-tri-tert-butylbenzene (mes*) derivative [Fe(mes*)(CO)2]⋅+ was fully characterized by XRD analysis, IR, NMR, cw-EPR, Mössbauer spectroscopy and cyclic voltammetry as the [Al(ORF)4]- (RF=C(CF3)3) salt. Chemical electronation, i. e., the single electron reduction, with decamethylferrocene generates neutral [Fe(mes*)(CO)2], whereas further deelectronation under CO-pressure leads to a dicationic three-legged [Fe(mes*)(CO)3]2+ salt with [Al(ORF)4]- counterion. The full substitution of the carbonyl ligands in [Fe(CO)5]⋅+[Al(ORF)4]- mainly resulted in disproportionation reactions, giving solid Fe(0) and the dicationic bis-arene salts [Fe(η6-arene)2]2+([Al(ORF)4]-)2 (arene=1,3,5-trimethylbenzene, benzene and fluorobenzene). Only by employing the very large fluoride bridged anion [F-{Al(ORF)3}2]-, it was possible to isolate an open shell bis-arene cation salt [Fe(C6H6)2]⋅+[F-{Al(ORF)3}2]-. The highly reactive cation was characterized by XRD analysis, cw-EPR, Mössbauer spectroscopy and cyclic voltammetry. The disproportionation of [Fe(C6H6)2]⋅+ salts to give solid Fe(0) and [Fe(C6H6)2]2+ salts was analyzed by a suitable cycle, revealing that the thermodynamic driving force for the disproportionation is a function of the size of the anion used and the polarity of the solvent.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:30 |
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| Enthalten in: |
Chemistry (Weinheim an der Bergstrasse, Germany) - 30(2024), 21 vom: 11. Apr., Seite e202400105 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Rall, Jan M [VerfasserIn] |
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| Links: |
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| Themen: |
Carbonyl cations |
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| Anmerkungen: |
Date Revised 11.04.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/chem.202400105 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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NLM367890925 |
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| 520 | |a © 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH. | ||
| 520 | |a Partial ligand substitution at the iron pentacarbonyl radical cation generates novel half-sandwich complexes of the type [Fe(η6-arene)(CO)2]⋅+ (arene=1,3,5-tri-tert-butylbenzene, 1,3,5-trimethylbenzene, benzene and fluorobenzene). Of those, the bulkier 1,3,5-tri-tert-butylbenzene (mes*) derivative [Fe(mes*)(CO)2]⋅+ was fully characterized by XRD analysis, IR, NMR, cw-EPR, Mössbauer spectroscopy and cyclic voltammetry as the [Al(ORF)4]- (RF=C(CF3)3) salt. Chemical electronation, i. e., the single electron reduction, with decamethylferrocene generates neutral [Fe(mes*)(CO)2], whereas further deelectronation under CO-pressure leads to a dicationic three-legged [Fe(mes*)(CO)3]2+ salt with [Al(ORF)4]- counterion. The full substitution of the carbonyl ligands in [Fe(CO)5]⋅+[Al(ORF)4]- mainly resulted in disproportionation reactions, giving solid Fe(0) and the dicationic bis-arene salts [Fe(η6-arene)2]2+([Al(ORF)4]-)2 (arene=1,3,5-trimethylbenzene, benzene and fluorobenzene). Only by employing the very large fluoride bridged anion [F-{Al(ORF)3}2]-, it was possible to isolate an open shell bis-arene cation salt [Fe(C6H6)2]⋅+[F-{Al(ORF)3}2]-. The highly reactive cation was characterized by XRD analysis, cw-EPR, Mössbauer spectroscopy and cyclic voltammetry. The disproportionation of [Fe(C6H6)2]⋅+ salts to give solid Fe(0) and [Fe(C6H6)2]2+ salts was analyzed by a suitable cycle, revealing that the thermodynamic driving force for the disproportionation is a function of the size of the anion used and the polarity of the solvent | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a carbonyl cations | |
| 650 | 4 | |a iron, transition metal | |
| 650 | 4 | |a weakly coordinating anions | |
| 700 | 1 | |a Nork, Leonie |e verfasserin |4 aut | |
| 700 | 1 | |a Engesser, Tobias A |e verfasserin |4 aut | |
| 700 | 1 | |a Mayländer, Maximilian |e verfasserin |4 aut | |
| 700 | 1 | |a Weber, Stefan |e verfasserin |4 aut | |
| 700 | 1 | |a Richert, Sabine |e verfasserin |4 aut | |
| 700 | 1 | |a Krossing, Ingo |e verfasserin |4 aut | |
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