The reactions of hydrogen cyanide and cyanogen halides XCN (X = H, Cl, Br, I) with arsenic and antimony pentafluoride result in the formation of 1:1 Lewis adducts, while the reactions with malononitrile CH2(CN)2 yielded both 1:1 and 1:2 Lewis adducts depending on the stoichiometry. In anhydrous hydrogen fluoride, the binary superacidic systems HF/AsF5 and HF/SbF5 are formed and protonation of the cyano-groups under formation of the corresponding nitrilium ions XCNH+ (R = Cl, Br, I) was observed. In addition, using HF/MF5, the preferred protonation site of dimethylcyanamide, Me2NCN was studied. All compounds were characterized by multinuclear NMR and vibrational spectroscopy and, in most cases, their X-ray crystal structures. The experimental work was supplemented by theoretical calculations.

Lewis adducts and protonation of nitriles

254th National Meeting (2017)

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