Abstract
Lewis acid-base adducts between AsF5 and the ketones, acetone, cyclopentanone, and adamantanone, were synthesized from SO2 and CH2Cl2 solutions. These adducts, which contain O---As pnictogen bonding interactions, were found to be stable in solutions at room temperature. Raman and NMR spectroscopy of the solid adducts showed a characteristic decrease in the C=O stretching frequency, as well as dramatic deshielding of the 13C resonance of the carbonyl group upon adduct formation. Fluorine-19 NMR spectroscopy showed the two fluorine environments of the O–AsF5 moiety. Optimization of the gas-phase geometry using DFT calculations yielded geometries with essentially planar CC=OAs moieties. NBO analyses of the adducts and the free ketones show the polarization of the C=O bond upon adduct formation. The lowering of the LUMO energies upon adduct formation is more dramatic than what was found for protonation of ketones and reflects the substantially enhanced electrophilicity of the adducted ketones.
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