Reactivity of collisionally activated dichlorocarbene dications studied by tandem mass spectrometry |
| |
Authors: | Bernard Leyh Dimitri Hautot |
| |
Institution: | 1. Département de Chimie Générale et de Chimie Physique, Institut de Chimie, Bātiment B6, Université de Liège, Liège 1, B. 4000, Sart-Tilman, Belgium
|
| |
Abstract: | The dissociation mechanisms of dichlorocarbene dications following collisional activation have been investigated via tandem mass spectrometric techniques and semi-empirical calculations. Three channels appear to be significant: {fx1019-1} The second channel becomes dominant at high internal energy. Production of ground state fragments (channel 1) involves a transition driven by spin—orbit coupling from the CCl 2 2+ $CCl_2^2 \tilde X^1 \Sigma _g^ + $ state to the CCl 2 2? ā3Σ u ? state en route to the fragments. The dissociation barrier for the production of ground state fragments from the ground electronic state of CCl 2 2+ via the spin—orbit-induced transition is equal to 420 kJ mol?1. The dissociation pathway that corresponds to channel 3 includes a first isomerization step from the linear Cl-C-Cl2+ structure to a bent Cl-Cl-C2+ connectivity. The calculated isomerization barrier amounts to 550 kJ mol?1. The calculated reverse activation barriers are compatible with the measured kinetic energy released on the fragments. |
| |
Keywords: | |
本文献已被 ScienceDirect SpringerLink 等数据库收录! |
|