title: Ab initio characterization of ring-opening H-transfer in ionized cyclopentanone: Similarity to ion-neutral complex-mediated alkane eliminations.
abstract: Ab initio procedures were used to characterize the transition states for α-cleavage and subsequent H-transfer starting with ionized cyclopentanone (1). The objective was to determine whether the parts of the ion disconnected by the bond cleavage remain in close association through the H-transfer. The transition state for C-C bond cleavage is close in energy to the resulting distonic ion, which is a stable species, and far in geometry from any transition state involving H-transfer. We find no evidence for any concertedness or "quasiconcertedness" in this reaction. Ring-opening H-transfer in 1 and ion-neutral complex-mediated alkane eliminations are compared.
authors.affiliation: Marine Biomedical Institute, University of Texas Medical Branch, 301 University Boulevard, 77555-1069, Galveston, TX.
authors.forename: C E
authors.initials: CE
authors.lastname: Hudson
authors.forename: D J
authors.initials: DJ
authors.lastname: McAdoo