Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 2, Pages 463-463Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202003847
Keywords
bond activation; chalcogens; ferrocenes; multinuclear NMR spectroscopy; phosphorus
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Tert-butyl-substituted diphospha[2]ferrocenophane was used as a stereochemically confined diphosphane to explore the addition of O, S, Se, and Te. Intermediates during rearrangement point to a disproportionation/synproportionation mechanism for the S and Se derivatives. Cyclic voltammetry and DFT studies indicate ferrocene-centred oxidation for most of the compounds presented.
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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