Interaction of Vinyl-Type Carbocations, C 3 H 5 + and C 4 H 7 + with Molecules of Water, Alcohols, and Acetone.

X-ray diffraction analysis and IR spectroscopy were used to study the products of the interaction of vinyl cations C 3 H 5 + and C 4 H 7 + (Cat + ) (as salts of carborane anion CHB 11 Cl 11 - ) with basic molecules of water, alcohols, and acetone that can crystallize from solutions in dichloromethane and C 6 HF 5 . Interaction with water, as content increased, proceeded via three-stages. (1) adduct Cat + ·OH 2 forms in which H 2 O binds (through the O atom) to the C=C + bond of the cation with the same strength as seen in the binding to Na in Na(H 2 O) 6 + . (2) H + is transferred from cation Cat + ·OH 2 to a water molecule forming H 3 O + and alcohol molecules (L) having the CH=CHOH entity. The O- atom of alcohols is attached to the H atom of the C=C + -H moiety of Cat + thereby forming a very strong asymmetric H-bond, (C=)C + -H⋅⋅⋅O. (3) Finally all vinyl cations are converted into alcohol molecule L and H 3 O + cations, yielding proton disolvates L-H + -L with a symmetric very strong H-bond. When an acetone molecule (Ac) interacts with Cat + , H + is transferred to Ac giving rise to a reactive carbene and proton disolvate Ac-H + -Ac. Thus, the alleged high reactivity of vinyl cations seems to be an exaggeration.