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Chalcogen‐Transfer Rearrangement: Exploring Inter‐ versus Intramolecular P−P Bond Activation

Franz, Roman
Nasemann, Sina
Bruhn, Clemens
Kelemen, Zsolt
Pietschnig, Rudolf

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.

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Gefördert im Rahmen des Projekts DEAL
Citation
In: Chemistry Volume 27 / Issue 2 (2020-07-17) , S. 641-648; EISSN 1521-3765
Collections
@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},
  keywords ={540 and Chemische Bindung and Aktivierung  and Chalkogene and Ferrocen and NMR-Spektroskopie and Phosphor},
  copyright  ={http://creativecommons.org/licenses/by/4.0/},
  language ={en},
  journal  ={Chemistry},
  year   ={2020-07-17}
}