Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 2, Pages 641-648Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202002481
Keywords
bond activation; chalcogens; ferrocenes; multinuclear NMR spectroscopy; phosphorus
Categories
Funding
- German Science Fund (DFG) [CRC 1319]
- Premium Postdoctoral Research Program 2019
- Projekt DEAL
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Stereochemically confined tert-butyl-substituted diphospha[2]ferrocenophane has been used to explore the addition of O, S, Se and Te, revealing a rearrangement mechanism that has been tracked through NMR spectroscopy and DFT calculations. Experimental results show a ferrocene-centred oxidation for most compounds.
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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