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.