From Phosphidic to Phosphonium? Umpolung of the P4‐Bonding Situation in [CpFe(CO)(L)(η1‐P4)]+ Cations (L=CO or PPh3)

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 corresp...

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Bibliographic Details
Published in:Chemistry : a European journal 2019-08, Vol.25 (45), p.10546-10551
Main Authors: Riddlestone, Ian M., Weis, Philippe, Martens, Arthur, Schorpp, Marcel, Scherer, Harald, Krossing, Ingo
Format: Article
Language:English
Subjects:
Bonding
Cations
Chemistry
clusters
Electrons
Iron
Phosphorus
Raman spectra
Raman spectroscopy
weakly coordinating anion (WCA)
white phosphorus (P4)
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Summary: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. Highly fluxional binding of P4 at room temperature has been characterized in electron‐poor cyclopentadienyl iron cations. Analysis of the bonding present in such systems is consistent with an umpolung in the Fe−P bond and their description as phosphonium complexes.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201902075