Reactivity of the CHBr2+ Dication toward Molecular Hydrogen

Jana Roithová (1, 2, 3) , Jan Zabka (1, 2) , Zdenek Herman (1, 2) , Roland Thissen (4) , Detlef Schröder (5) , Helmut Schwarz (5)

1 V. Čermák Laboratory
2 J. Heyrovský Institute of Physical Chemistry
3 IOCB / CAS - Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences
4 LCPO - Laboratoire de Chimie Physique D'Orsay
5 Institut für Chemie

Structural aspects as well as the stability and reactivity of the CHBr2+ dication are studied both experimentally and theoretically. Translational energy distributions of the CHBr+ products from charge transfer between CHBr2+ and Kr indicate that the dication exists in two isomeric forms, H−C−Br2+ and C−Br−H2+. In the reaction of CHBr2+ with H2, the dominant channel corresponds to proton transfer leading to CBr+ + H3+. Other reaction channels involve the formation of the intermediates CH3Br2+ and CH2BrH2+, respectively. Both of the latter dications can either lose a proton to form CH2Br+ 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.

Jana Roithová, Jan Zabka, Zdenek Herman, Roland Thissen, Detlef Schröder, et al.. Reactivity of the CHBr2+ Dication toward Molecular Hydrogen. Journal of Physical Chemistry A, 2006, 110 (20), pp.6447-6453. ⟨10.1021/jp0610719⟩. ⟨insu-00367316⟩