A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines
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In: Chemistry – A European Journal Volume 29 / Issue 68 (2023-08-31) , S. ; eissn:1521-3765
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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.
@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}, keywords ={540 and Autoxidation and Phosphine and Sauerstoff and Chemische Eigenschaft}, copyright ={http://creativecommons.org/licenses/by/4.0/}, language ={en}, journal ={Chemistry – A European Journal}, year ={2023-08-31} }