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.
ABSTRACT
Bare metal anions K(-), Rb(-), Cs(-), Fe(-), Co(-), Ni(-), Cu(-), and Ag(-), generated by electrospray ionization of the corresponding oxalate or tricarballylate solutions, were allowed to react with methyl and ethyl chloride, methyl bromide, nitromethane, and acetonitrile in the collision hexapole of a triple-quadrupole mass spectrometer. Observed reactions include (a) the formation of halide, nitride, and cyanide anions, which was shown to be likely due to the insertion of the metal into the C-X, C-N, and C-C bonds, (b) transfer of H(+) from the organic molecule, which is demonstrated to most likely be due to the simple transfer of a proton to form neutral metal hydride, and (c) in the case of nitromethane, direct electron transfer to form the nitromethane radical anion. Interestingly, Co(-) was the only metal anion to transfer an electron to acetonitrile. Differences in the reactions are related to the differences in electron affinity of the metals and the Δ(acid)H° of the metals and organic substrates. Density functional theory calculations at the B3-LYP/6-311++G(3df,2p)//B3-LYP/6-31+G(d) level of theory shed light on the relative energetics of these processes and the mechanisms by which they take place.
