Gas-phase reactions of Fe+ with ketones and ethers

A pulsed laser has been used in conjunction with an ion cyclotron resonance spectrometer to generate and study the gas-phase ion-molecule reactions of Fe+ with simple carbonyl compounds and ethers. Oxidative addition reactions are observed, producing alkyl acyl, and alkoxide intermediates which undergo intramolecular rearrangement by a β-hydride shift mechanism. Decarbonylation reactions are observed with only a few small ketones. The main reaction channel is dehydrogenation for unbranched ketones and reductive elimination of methane for those branched at the α carbon. Reactions of Fe+ with diisopropyl ketone, cyclohexanone, cyclopentanone, and tetrahydrofuran suggest the existence of intermediate and stable π-ally complexes resulting from sequential β-hydride shifts