title: Hydrogen atom tunneling in triplet o-methylbenzocycloalkanones: effects of structure on reaction geometry and excited state configuration.
abstract: The rates of phosphorescence decay of 4,7-dimethylindanone (2), 6,9-dimethylbenzosuberone (3), and several related compounds have been analyzed between 4 and 100 K to determine the contributions of intramolecular hydrogen atom tunneling from the o-methyl group to the excited state carbonyl oxygen. Changes in the benzocycloalkanone ring size from five to seven not only affect the geometry at the reaction center, but they also affect the electronic configuration of the triplet excited state in a significant manner. While the triplet state of 5,8-dimethyltetralone (1) in nonpolar glasses can be clearly described as having a predominant n,pi configuration, compounds 2 and 3 have a significantly larger contribution of the less reactive pi,pi state. 4,7-Dimethylindanone (2) is stable under cryogenic conditions and in solution at ambient temperature. In contrast, triplet lifetimes and product analysis indicate that 6,9-dimethylbenzosuberone (3) reacts by quantum mechanical tunneling at temperatures as low as 4 K. A surprisingly small isotope effect k(H)/k(D) approximately 1.1 between 4 and 50 K increases steadily up to k(H)/k(D) approximately 5.1 at 100 K. This unusual observation is interpreted in terms of a vibrationally activated quantum mechanical tunneling process with hydrogen atom transfer at the lowest temperatures being mediated by zero-point-energy reaction-promoting skeletal motions. Results presented here indicate that the combined effects of increasing pi,pi character and unfavorable reaction geometry contribute to the diminished reactivity of o-methyl ketones 2 and 3 as compared to those of tetralone 1.