Aufsatz
Deutsche Forschungsgemeinschaft; Hessisches Ministerium für Wissenschaft und Kunst
A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines
Abstract
A general approach for increasing the air-stability of various primary phosphines in the absence of kinetic stabilization is presented that contrasts with previous interpretations, which were limited to specific phosphines. This contribution shows the synthesis of a series of air-stable primary phosphines Fc(CH₂)nPH₂, where n=0,1,2,3; and Fc=ferrocenyl, and their corresponding isolable primary phosphine oxides. It was demonstrated that the ferrocene moiety exerts an antioxidant effect on the primary phosphine group, which is intermolecular, solvent dependent and increases with the electron density on the ferrocene moiety. Furthermore, we demonstrated that the presence of ferrocene in solution also inhibits the oxidation of other secondary and tertiary phosphines in air. Together our findings suggest that quenching of singlet oxygen is the actual reason for the antioxidant effect; this was experimentally confirmed by using other established singlet oxygen quenchers, thus demonstrating a key role of singlet oxygen in the aerobic oxidation of phosphines.
Citation
In: Chemistry – A European Journal Volume 29 / Issue 68 (2023-08-31) eissn:1521-3765Sponsorship
Gefördert im Rahmen des Projekts DEALDeutsche Forschungsgemeinschaft; Hessisches Ministerium für Wissenschaft und Kunst
Citation
@article{doi:10.17170/kobra-202312129213,
author={Horký, Filip and Franz, Roman and Bruhn, Clemens and Pietschnig, Rudolf},
title={A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines},
journal={Chemistry – A European Journal},
year={2023}
}
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2024-02-07T13:31:11Z 2024-02-07T13:31:11Z 2023-08-31 doi:10.17170/kobra-202312129213 http://hdl.handle.net/123456789/15442 Gefördert im Rahmen des Projekts DEAL Deutsche Forschungsgemeinschaft; Hessisches Ministerium für Wissenschaft und Kunst eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ autoxidation primary phosphines primary phosphine oxides singlet oxygen quenching 540 A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines Aufsatz A general approach for increasing the air-stability of various primary phosphines in the absence of kinetic stabilization is presented that contrasts with previous interpretations, which were limited to specific phosphines. This contribution shows the synthesis of a series of air-stable primary phosphines Fc(CH₂)nPH₂, where n=0,1,2,3; and Fc=ferrocenyl, and their corresponding isolable primary phosphine oxides. It was demonstrated that the ferrocene moiety exerts an antioxidant effect on the primary phosphine group, which is intermolecular, solvent dependent and increases with the electron density on the ferrocene moiety. Furthermore, we demonstrated that the presence of ferrocene in solution also inhibits the oxidation of other secondary and tertiary phosphines in air. Together our findings suggest that quenching of singlet oxygen is the actual reason for the antioxidant effect; this was experimentally confirmed by using other established singlet oxygen quenchers, thus demonstrating a key role of singlet oxygen in the aerobic oxidation of phosphines. open access Horký, Filip Franz, Roman Bruhn, Clemens Pietschnig, Rudolf doi:10.1002/chem.202302518 Grant Number: HO7221/1-1; Grant Number: LOEWE SMolBits Autoxidation Phosphine Sauerstoff Chemische Eigenschaft publishedVersion eissn:1521-3765 Issue 68 Chemistry – A European Journal Volume 29 false e202302518
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