Interaction of Vinyl-Type Carbocations, CH and CH 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 CH and CH (Cat) (as salts of carborane anion CHBCl) with basic molecules of water, alcohols, and acetone that can crystallize from solutions in dichloromethane and CHF. Interaction with water, as content increased, proceeded via three-stages. (1) adduct Cat·OH forms in which HO 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(HO). (2) H is transferred from cation Cat·OH to a water molecule forming HO 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 HO 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.