Datum
2020-07-17Schlagwort
540 Chemie Chemische BindungAktivierung <Chemie>ChalkogeneFerrocenNMR-SpektroskopiePhosphorMetadata
Zur Langanzeige
Aufsatz
Chalcogen‐Transfer Rearrangement: Exploring Inter‐ versus Intramolecular P−P Bond Activation
Zusammenfassung
tert‐Butyl‐substituted diphospha[2]ferrocenophane has been used as a stereochemically confined diphosphane to explore the addition of O, S, Se and Te. Although the diphosphanylchalcogane has been obtained for tellurium, all other chalcogens give diphosphane monochalcogenides. The latter transform via chalcogen‐transfer rearrangement to the corresponding diphosphanylchalcoganes upon heating. The kinetics of this rearrangement has been followed with NMR spectroscopy supported by DFT calculations. Intermediates during rearrangement point to a disproportionation/synproportionation mechanism for the S and Se derivatives. Cyclic voltammetry together with DFT studies indicate ferrocene‐centred oxidation for most of the compounds presented.
Zitierform
In: Chemistry Volume 27 / Issue 2 (2020-07-17) , S. 641-648 ; EISSN 1521-3765Förderhinweis
Gefördert im Rahmen des Projekts DEALZitieren
@article{doi:10.17170/kobra-202101213012,
author={Franz, Roman and Nasemann, Sina and Bruhn, Clemens and Kelemen, Zsolt and Pietschnig, Rudolf},
title={Chalcogen‐Transfer Rearrangement: Exploring Inter‐ versus Intramolecular P−P Bond Activation},
journal={Chemistry},
year={2020}
}
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2021-01-22T11:08:00Z 2021-01-22T11:08:00Z 2020-07-17 doi:10.17170/kobra-202101213012 http://hdl.handle.net/123456789/12433 Gefördert im Rahmen des Projekts DEAL eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ bond activation chalcogens ferrocenes multinuclear NMR spectroscopy phosphorus 540 Chalcogen‐Transfer Rearrangement: Exploring Inter‐ versus Intramolecular P−P Bond Activation Aufsatz tert‐Butyl‐substituted diphospha[2]ferrocenophane has been used as a stereochemically confined diphosphane to explore the addition of O, S, Se and Te. Although the diphosphanylchalcogane has been obtained for tellurium, all other chalcogens give diphosphane monochalcogenides. The latter transform via chalcogen‐transfer rearrangement to the corresponding diphosphanylchalcoganes upon heating. The kinetics of this rearrangement has been followed with NMR spectroscopy supported by DFT calculations. Intermediates during rearrangement point to a disproportionation/synproportionation mechanism for the S and Se derivatives. Cyclic voltammetry together with DFT studies indicate ferrocene‐centred oxidation for most of the compounds presented. open access Franz, Roman Nasemann, Sina Bruhn, Clemens Kelemen, Zsolt Pietschnig, Rudolf doi:10.1002/chem.202002481 Chemische Bindung Aktivierung <Chemie> Chalkogene Ferrocen NMR-Spektroskopie Phosphor publishedVersion EISSN 1521-3765 Issue 2 Chemistry 641-648 Volume 27 false
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