Experimental and theoretical study of the photochemical and thermal decomposition of maleic and dichloromaleic anhydrides

The photochemical and thermal behavior of maleic anhydride 1a and dichloromaleic anhydride 1b, in cryogenic matrix were investigated by means of FT-IR spectroscopy. The ketenylcarbenes represent the key intermediate in the decomposition processes of the anhydrides, even if they were not observed experimentally. The yields of the different products depend on the thermal or photochemical reaction conditions. The main photochemical products obtained from 1a were cyclopropenone and acetylene, whereas the major products from 1b were dichlorocyclopropenone and dichloroacetylene, along with small quantities of dichloropropadienone. The thermal reaction leads to dichloro propa dienone, CO, and CO2. MO calculations performed at the HF/6-31G*//HF/6-31G* level support the experimental mechanisms.Key words: photolysis, thermolysis, ab initio calculations, cryogenic matrix, ketenylcarbenes.