A Ferrocenophane-Based Diaminophosphenium Ion

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http://hdl.handle.net/10138/322380

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Weller , S , Schlindwein , S H , Feil , C M , Kelemen , Z , Buzsaki , D , Nyulaszi , L , Isenberg , S , Pietschnig , R , Nieger , M & Gudat , D 2019 , ' A Ferrocenophane-Based Diaminophosphenium Ion ' , Organometallics , vol. 38 , no. 24 , pp. 4717-4725 . https://doi.org/10.1021/acs.organomet.9b00701

Title: A Ferrocenophane-Based Diaminophosphenium Ion
Author: Weller, Stefan; Schlindwein, Simon H.; Feil, Christoph M.; Kelemen, Zsolt; Buzsaki, Daniel; Nyulaszi, Laszlo; Isenberg, Stefan; Pietschnig, Rudolf; Nieger, Martin; Gudat, Dietrich
Contributor: University of Helsinki, Department of Chemistry
Date: 2019-12-23
Language: eng
Number of pages: 9
Belongs to series: Organometallics
ISSN: 0276-7333
URI: http://hdl.handle.net/10138/322380
Abstract: Reactions of P-chloro-1,3,2-diazaphospha[3]ferrocenophanes with ECl3 (E = Al, Ga) under solvent-free conditions and with Na[Mn(CO)(5)] furnished salts featuring a ferrocenophane-based phosphenium cation and neutral phosphenium complexes, respectively. All products were characterized by spectroscopic studies. Single-crystal X-ray diffraction studies confirmed the ionic nature of the phosphenium tetrachloroaluminate and the structural analogy between the phosphenium complexes and Fischer-type carbene complexes. Distinct deviations in the conformation of the ansa bridge suggest electronic stabilization of the electrophilic phosphorus atom by phosphorus-nitrogen pi interactions in the free cation and by phosphorus-metal pi bonding in the complexes. The observation of short intermolecular contacts in the crystalline phosphenium salt and its chemical behavior toward donor solvents attest to the cation having an unusually high degree of Lewis acidity, which was confirmed by DFT studies and related to the presence of a rather large N-P-N angle. Computational studies indicate further that the free phosphenium cation exhibits a closed-shell electronic structure with a formal Fe(II) oxidation state and is thus a true analogue to ferrocenophane-based diaminotetrylenes.
Subject: N-HETEROCYCLIC PHOSPHENIUM
PHOSPHORUS-COMPOUNDS
CHEMICAL-SHIFTS
METAL-COMPLEXES
CHEMISTRY
CATIONS
LIGANDS
STABILITIES
REACTIVITY
BONDS
116 Chemical sciences
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