title: The reactivity of the 1,4-biradical formed by Norrish type reactions of aqueous valerophenone: a QM/MM-based FEP study.
abstract: In the present work, Norrish type reactions of aqueous valerophenone and the reactivity of the triplet 1,4-biradical formed by the 1,5-H shift have been studied with the free energy perturbation (FEP) method that is based on the combined scheme of quantum mechanics (QM) and molecular mechanics (MM). The fluctuation and diffusion of the solvent molecules were found to have an important influence on Norrish type reactions of valerophenone. The α C-C bond cleavages were predicted to be not in competition with the 1,5-H shift, which is consistent with the experimental findings that Norrish type II quantum yield is close to unity. The triplet lifetime of aqueous valerophenone was experimentally inferred to be 52 ns, which is nearly reproduced by the QM/MM-FEP calculated rate constant of 2.33 × 10(7) s(-1). The calculated results show that branch ratios of the subsequent reactions from the triplet 1,4-biradical are mainly controlled by the equilibrium populations of its stable conformations. The ratio of cleavage to cyclization measured experimentally is well reproduced by the present QM/MM-FEP calculations. However, the absolute quantum yields of cleavage and cyclization reactions are underestimated theoretically and the reason for this is discussed.
authors.affiliation: Beijing Normal University, China.
authors.forename: Lin
authors.initials: L
authors.lastname: Shen
authors.forename: Wei-Hai
authors.initials: WH
authors.lastname: Fang