Gas-phase reactions of Sc+, Y+, and Lu+ with alcohols. Effects of the class and chain length of alcohols on the nature of primary products

The primary gas-phase reactions between methanol, ethanol, propan-1-ol, propan-2-ol, and 2-methyipropan-2-ol and the isovalent rare earth metal ions Sc⁺, Y⁺, and Lu⁺ generated by laser desorption-ionization of metal targets have been investigated by using a Fourier transform ion cyclotron resonance mass spectrometer. The three metal ions react exothermically with all the alcohols. The overall reactivity is controlled by the high oxophilicity of these metals, and the primary metallated ions obtained are principally oxygenated species. However, the number and the nature of these primary products depends on the electronic configuration of the metal ions as well as on the class and the principal chain length of alcohols. The order of reactivity is Y⁺ > Sc⁺ > Lu⁺. The Y⁺ and Sc⁺ ions principally react via C—O and O—H insertions, whereas Lu+ reacts by direct abstraction or via various five-center electrocyclic mechanisms as a function of the class and the alcohol chain length.