title: Reactivity of the CHBr2+ dication toward molecular hydrogen.
abstract: Structural aspects as well as the stability and reactivity of the CHBr(2+) dication are studied both experimentally and theoretically. Translational energy distributions of the CHBr(+) products from charge transfer between CHBr(2+) and Kr indicate that the dication exists in two isomeric forms, H-C-Br(2+) and C-Br-H(2+). In the reaction of CHBr(2+) with H(2), the dominant channel corresponds to proton transfer leading to CBr(+) + H(3)(+). Other reaction channels involve the formation of the intermediates CH(3)Br(2+) and CH(2)BrH(2+), respectively. Both of the latter dications can either lose a proton to form CH(2)Br(+) or undergo a spin-isomerization followed by cleavage of the C-Br bond. The proposed mechanisms are supported by DFT calculations and deuterium labeling experiments.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo n. 2, 166 10 Prague, Czech Republic. jana.roithova@uochb.cas.cz
authors.forename: Jana
authors.initials: J
authors.lastname: Roithová
authors.forename: Ján
authors.initials: J
authors.lastname: Zabka
authors.forename: Zdenek
authors.initials: Z
authors.lastname: Herman
authors.forename: Roland
authors.initials: R
authors.lastname: Thissen
authors.forename: Detlef
authors.initials: D
authors.lastname: Schröder
authors.forename: Helmut
authors.initials: H
authors.lastname: Schwarz