Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental impor...Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental importance in understanding the underlying mechanism of their atmospheric reactions.In sharp contrast to the intensively studied parent molecule(CH_(2)OO)and the alkyl-substituted derivatives,the knowledge about the fluorinated analogue CF_(3)C(H)OO is scarce.By carefully heating the triplet carbene CF_(3)CH in an O2-doped Ar-matrix to 35 K,the elusive carbonyl oxide CF_(3)C(H)OO in syn-and anti-conformations has been generated and characterized with infrared(IR)and ultraviolet-visible(UV-vis)spectroscopy.The spectroscopic identification is supported by^(18)O-labeling experiments and quantum chemical calculations at the B3 LYP/6-311++G(3df,3pd)and MP2/6-311++G(2d,2p)levels.Upon the long-wavelength irradiation(λ>680 nm),both conformers of CF_(3)C(H)OO decompose to give trifluoroacetaldehyde CF_(3)C(H)O and simultaneously rearrange to the isomeric dioxirane,cyclic-CF_(3)CH(OO),which undergoes isomerization to the lowest-energy carboxylic acid CF_(3)C(O)OH upon UV-light excitation at 365 nm.The O_(2)-oxidation of CF_(3)CH via the intermediacy of CF_(3)C(H)OO and cyclic-CF_(3)CH(OO)might provide new insight into the mechanism for the degradation of hydro-chlorofluorocarbon CF_(3)CHCl_(2)(HCFC-123)in the atmosphere.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22003010 and 22025301)
文摘Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental importance in understanding the underlying mechanism of their atmospheric reactions.In sharp contrast to the intensively studied parent molecule(CH_(2)OO)and the alkyl-substituted derivatives,the knowledge about the fluorinated analogue CF_(3)C(H)OO is scarce.By carefully heating the triplet carbene CF_(3)CH in an O2-doped Ar-matrix to 35 K,the elusive carbonyl oxide CF_(3)C(H)OO in syn-and anti-conformations has been generated and characterized with infrared(IR)and ultraviolet-visible(UV-vis)spectroscopy.The spectroscopic identification is supported by^(18)O-labeling experiments and quantum chemical calculations at the B3 LYP/6-311++G(3df,3pd)and MP2/6-311++G(2d,2p)levels.Upon the long-wavelength irradiation(λ>680 nm),both conformers of CF_(3)C(H)OO decompose to give trifluoroacetaldehyde CF_(3)C(H)O and simultaneously rearrange to the isomeric dioxirane,cyclic-CF_(3)CH(OO),which undergoes isomerization to the lowest-energy carboxylic acid CF_(3)C(O)OH upon UV-light excitation at 365 nm.The O_(2)-oxidation of CF_(3)CH via the intermediacy of CF_(3)C(H)OO and cyclic-CF_(3)CH(OO)might provide new insight into the mechanism for the degradation of hydro-chlorofluorocarbon CF_(3)CHCl_(2)(HCFC-123)in the atmosphere.
