The oxidation pathways of Ti+ by acetaldehyde in the gas phase: A density functional theory investigation

Oxidation of Ti+ (4F and 2F) with acetaldehyde is investigated using density functional theory. Geometries and energies of the reactants, intermediates and products involved in the reaction are located. Our calculations indicate that oxidation occurring on both the quartet and doublet potential energy surfaces starts with encounter complexation followed by three possible pathways: metal-mediated H migration, direct methyl H shift, and/or C–O insertion. The doublet pathways through intersystem crossing from the quartet ground-state reactants are always energetically preferable with respect to the corresponding quartet routes and the most energetically favorable oxidation occurs through C–O insertion on the doublet surface.