The dehydrogenation of alcohols and hydrocarbons by atomic metal anions

Abstract

The reactivity of anionic metal-carbonyl systems toward hydrocarbons, alcohols and a variety of other classes of molecules is well established in the literature. In this study we explored the reactions of atomic metal anions M(-), notably K(-), Cs(-), Co(-), Fe(-), Cu(-) and Ag(-), with alcohols, alkanes, alkenes and alkynes. All of the metal anions deprotonated the alcohols and alkynes. Also observed were the subsequent reactions of the resulting organic anions. Fe(-) and Cu(-) consistently displayed mono- and bis-dehydrogenation of primary and secondary alcohols, and alkanes, alkenes and alkynes to form MH(-) and MH(2)(-). Mechanisms for the dehydrogenation reactions are proposed and substantiated with isotopically-labelled reagents and thermochemical arguments.