Reactivity of the CHBr2+ dication toward molecular hydrogen.
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.
Roithová
Jana
J
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
Zabka
Ján
J
Herman
Zdenek
Z
Thissen
Roland
R
Schröder
Detlef
D
Schwarz
Helmut
H