title: 2-(3,5-Dinitrophenyl)-1,3-dithiane carbanion: a benzylic anion with a low energy triplet state.
abstract: Calculations at the DFT level predict that benzyl anions with strong π-electron-withdrawing groups in the meta position(s) have low energy diradical or triplet electronic states. Specifically, the 2-(3,5-dinitrophenyl)-1,3-dithiane carbanion is predicted to have nearly degenerate singlet and triplet states at the (U)B3LYP level as a free anion. Its lithium ion pair is predicted to be a ground-state triplet with a substantial (26 kcal/mol) singlet-triplet energy gap. Experiments on this anion using chemical trapping, NMR, and the Evans method strongly suggest that this anion is either a triplet or a ground-state singlet with a very low energy triplet state.
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742-2021, United States.
authors.forename: Raffaele R
authors.initials: RR
authors.lastname: Perrotta
authors.forename: Arthur H
authors.initials: AH
authors.lastname: Winter
authors.forename: William H
authors.initials: WH
authors.lastname: Coldren
authors.forename: Daniel E
authors.initials: DE
authors.lastname: Falvey