title: Mechanistic Information from Nonstationary Points.
abstract: The thermal cyclization of enyne-carbodiimides substituted at both the alkyne and carbodiimide terminus showed two curved Hammett correlations (log k/k0 against σp) that were fully reproduced by DFT (density functional theory) computational results. The latter suggest a concerted mechanism, but the transition state (TS) analysis failed to reveal any mechanistic insight about the reason for a curved Hammett correlation. Instead a preTS inspection, i.e., examination of the electronic and steric details on route between reactant and TS, furnished a detailed picture of the mechanism.
authors.affiliation: Department of Chemistry and Biology, Organische Chemie 1, Universität Siegen , Adolf-Reichwein-Strasse 2, D-57068 Siegen, Germany.
authors.forename: Anup
authors.initials: A
authors.lastname: Rana
authors.affiliation: Department of Chemistry and Biology, Organische Chemie 1, Universität Siegen , Adolf-Reichwein-Strasse 2, D-57068 Siegen, Germany.
authors.forename: M Emin
authors.initials: ME
authors.lastname: Cinar
authors.affiliation: Department of Chemistry and Biology, Organische Chemie 1, Universität Siegen , Adolf-Reichwein-Strasse 2, D-57068 Siegen, Germany.
authors.forename: Debabrata
authors.initials: D
authors.lastname: Samanta
authors.affiliation: Department of Chemistry and Biology, Organische Chemie 1, Universität Siegen , Adolf-Reichwein-Strasse 2, D-57068 Siegen, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Schmittel