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The Bis(ferrocenyl)phosphenium Ion Revisited
Author(s) -
Olaru Marian,
Mischin Alexandra,
Malaspina Lorraine A.,
Mebs Stefan,
Beckmann Jens
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201913081
Subject(s) - chemistry , lewis acids and bases , intramolecular force , divalent , ion , acceptor , imidazole , medicinal chemistry , stereochemistry , catalysis , organic chemistry , physics , condensed matter physics
Abstract The bis(ferrocenyl)phosphenium ion, [Fc 2 P] + , reported by Cowley et al. ( J. Am. Chem. Soc . 1981 , 103 , 714–715), was the only claimed donor‐free divalent phosphenium ion. Our examination of the molecular and electronic structure reveals that [Fc 2 P] + possesses significant intramolecular Fe⋅⋅⋅P contacts, which are predominantly electrostatic and moderate the Lewis acidity. Nonetheless, [Fc 2 P] + undergoes complex formation with the Lewis bases PPh 3 and IPr to give the donor–acceptor complexes [Fc 2 P(PPh 3 )] + and [Fc 2 P(IPr)] + (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazole‐2‐ylidene).