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Lewis Base Free Oxophosphonium Ions: Tunable, Trigonal-Planar Lewis Acids.

Marius A WünscheTim WittelerFabian Dielmann
Published in: Angewandte Chemie (International ed. in English) (2018)
Oxophosphonium ions (R2 P=O)+ are fascinating chemical intermediates related to the well-known acylium cations (RC=O)+ , and comprise a tricoordinate phosphorus(V) center with a phosphorus-oxygen double bond. Here, we report the synthesis of two oxophosphonium ions stabilized by bulky imidazolin-2-imine and imidazolin-2-olefin substituents attached to phosphorus. The novel species were characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis, and the bonding situation was probed by DFT calculations. Determination of the acceptor number and the fluoride ion affinity revealed that the choice of the substituents has a strong influence on the electrophilicity of the phosphorus center. Additionally, the formation of Lewis base adducts with pyridine derivatives and the reactivity with isopropyl alcohol was explored.
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