title: Secondary alpha isotope effects on deuterium tunneling in triplet o-methylanthrones: extraordinary sensitivity to barrier width.
abstract: The rates of deuterium transfer in the photoenolization of triplet 1,4-dimethyl-10H-anthracen-9-one (1) with varying degrees of deuterium label in their methyl groups (1-d3, 1-d2, and 1-d) have been investigated as a function of temperature between 5 and 77 K. Measurable rate constants in the case of 1-d3 and 1-d2 were used to construct Arrhenius plots which illustrate the expected curvature and leveling off of rate constant versus temperature. The difference in tunneling rate constants of 1-d3 and 1-d2 yields a tunneling isotope effect, TIE = 2.4, which is attributed to the secondary alpha isotopic substitution. Density functional theory (DFT, B3LYP/6-31G*) calculations were carried out to obtain structural and energetic information for the H(D) transfer along the triplet state zero-point energy levels. The temperature dependence of the rate constants for each isotopologue was simulated with a model that considers the frequency of the C-D stretching mode and the quantum mechanical permeability determined from calculated energy parameters. The model suggests that a difference in barrier width of only 0.015 A between 1-d3 and 1-d2 leads to the observed 2-fold difference between tunneling rates.
authors: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
authors: Luis M
authors: LM
authors: Campos
authors: Manoj V
authors: MV
authors: Warrier
authors: Krisztina
authors: K
authors: Peterfy
authors: K N
authors: KN
authors: Houk
authors: Miguel A
authors: MA
authors: Garcia-Garibay