Oxidation of tert-butyl alcohol to isobutylene oxide on a Ag(110) surface: The role of unactivated C-H bonds in product selectivity

Article abstract of DOI:10.1021/ja00193a012

Tert-Butyl alcohol reacts with oxygen-covered Ag(110) surfaces below 200 K yielding t-BuO_(a) and adsorbed water and hydroxyl groups. Temperature-programmed reaction spectroscopy demonstrates that t-BuO_(a) reacts at 440 and 510 K by processes that involve rate-limiting C-H bond cleavage yielding isobutylene oxide, isobutylene, tert-butyl alcohol, H₂O, and CO₂. The reaction path at 440 K predominates when the initial coverage of O_(a) is high; that at 510 K predominates when the coverage of O_(a) is low. A third process occurs at 590 K, producing acetone. It is concluded from this work that the unactivated methyl C-H bonds in t-BuO_(a) are significantly more stable toward cleavage by this surface than are the activated C-H bonds in MeO_(a) or EtO_(a).