The thermal chemistry of 2-propanol and 2-propyl iodide on clean and oxygen-pretreated Ni(100) single-crystal surfaces was studied by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and reflection-absorption infrared spectroscopy (RAIRS). 2-Propyl iodide was used as a precursor for the preparation of 2-propyl surface species, in analogy to chemistry reported for other halo hydrocarbons. Those 2-propyl groups were shown to convert to acetone on both oxygen- and hydroxide-covered Ni(100) surfaces by following a two step mechanism, starting with a facile oxygen insertion into the metal-alkyl bond. The resulting 2-propoxide surface moiety, an intermediate that can also be prepared via dehydrogenation of the hydroxyl group in adsorbed 2-propanol, is stable up to about 300 K, at which point it undergoes P-hydride elimination to acetone. Coadsorbed surface hydroxide facilitates the first oxygen insertion reaction, and surface oxygen enhances the latter conversion of 2-propoxide to acetone. Some alcohol dehydration to propene is also observed, presumably by reaction of two hydrogen-bonded alcohol molecules. These results point to the feasibility of designing nickel-based catalysts for the selective partial oxidation of hydrocarbons.