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The Bis(ferrocenyl)phosphenium Ion Revisited.


ABSTRACT: The bis(ferrocenyl)phosphenium ion, [Fc2 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 [Fc2 P]+ possesses significant intramolecular Fe???P contacts, which are predominantly electrostatic and moderate the Lewis acidity. Nonetheless, [Fc2 P]+ undergoes complex formation with the Lewis bases PPh3 and IPr to give the donor-acceptor complexes [Fc2 P(PPh3 )]+ and [Fc2 P(IPr)]+ (IPr=1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene).

SUBMITTER: Olaru M 

PROVIDER: S-EPMC7003730 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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The Bis(ferrocenyl)phosphenium Ion Revisited.

Olaru Marian M   Mischin Alexandra A   Malaspina Lorraine A LA   Mebs Stefan S   Beckmann Jens J  

Angewandte Chemie (International ed. in English) 20191216 4


The bis(ferrocenyl)phosphenium ion, [Fc<sub>2</sub> P]<sup>+</sup> , 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<sub>2</sub> P]<sup>+</sup> possesses significant intramolecular Fe⋅⋅⋅P contacts, which are predominantly electrostatic and moderate the Lewis acidity. Nonetheless, [Fc<sub>2</sub> P]<sup>+</sup> undergoes complex formation with the  ...[more]

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