Dr. Marian Olaru, Alexandra Mischin, Lorraine A. Malaspina, Dr. Stefan Mebs, Prof. Dr. Jens Beckmann
Angewandte Chemie- International Edition (2020) 59, Pages 1581-1584
The bis(ferrocenyl)phosphenium ion, [Fc2P]+, 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 [Fc2P]+ possesses significant intramolecular Fe⋅⋅⋅P contacts, which are predominantly electrostatic and moderate the Lewis acidity. Nonetheless, [Fc2P]+ undergoes complex formation with the Lewis bases PPh3 and IPr to give the donor–acceptor complexes [Fc2P(PPh3)]+ and [Fc2P(IPr)]+ (IPr=1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene).