Abstract
Upon coordinating P4 to electron poor cyclopentadienyl-iron cations, the average P-P bond distances shrink and the respective P4 breathing mode in the Raman spectra (600 cm-1 , P4, free ) is blueshifted by >40 cm-1 in [CpFe(CO)(L)(η1 -P4 )]+ cations (L=CO or PPh3 ). Analysis suggests that this corresponds to an umpolung of the bonding from more phosphidic in the known, electron-rich systems to more phosphonium-like in the reported electron-poor versions. This may open new functionalization pathways for white phosphorus P4 .
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