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

• Published in: Chemistry : a European journal Vol. 27; no. 2; pp. 641 - 648
• Main Authors: Franz, Roman, Nasemann, Sina, Bruhn, Clemens, Kelemen, Zsolt, Pietschnig, Rudolf
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 07.01.2021; John Wiley and Sons Inc
• Subjects: bond activation; chalcogens; Chemistry; Disproportionation; ferrocenes; Intermediates; Magnetic resonance spectroscopy; multinuclear NMR spectroscopy; NMR; NMR spectroscopy; Nuclear magnetic resonance; Oxidation; phosphorus; Tellurium; bond activation; ferrocenes; chalcogens; multinuclear NMR spectroscopy; phosphorus
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202002481

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. Chalcogen transfer: Investigation of the addition of O, S, Se and Te to a model diphosphane and subsequent thermal rearrangement point to a disproportionation/synproportionation mechanism (see scheme).