Abstract
, an elusive photo-isomer of , has been observed in matrix IR spectra from the precursors exposed to radiation from laser ablation of transition-metals. Other plausible products, and are not detected due to their considerably higher energies. Parallel to its previously reported analogues, the C-X bonds are considerably stronger than those of the reactant, and particularly the Cl atom that is weakly bound to the residual Cl atom forms an unusually strong carbon-halogen bond. NBO analysis reveals that the C-Cl bond is a true double bond, and the weak bond is largely ionic, . IRC computation reproduces smooth inter-conversion between the reactant and product, and the transition state is energetically close to the product, consistent with its prompt disappearance in the early stage of photolysis.
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