Dihalogenated Methylperoxy Radicals: Spectroscopic Characterization and Photodecomposition by Release of HOC

Bo Lu^a, Chao Song^a, Jie Liu^a, Tarek Trabelsi ^b,Joseph S. Francisco^*b, Lina Wang^c, and Xiaoqing Zeng^*ac（曾小庆）  

^aCollege of Chemistry, Chemical Engineering and Materials Science,Soochow University, Suzhou 215123 (P. R. China)

^bDepartment of Earth and Environmental Science and Department of Chemistry, University of Pennsylvania, Pennsylvania 19104 (USA)

^cDepartment of Chemistry, Fudan University, Shanghai 200433 (P. R. China)

 Chem. Eur. J. 2020, 26, 2817--2820

Two atmospherically relevant dihalogenated methylperoxy radicals CHX₂OO^. (X=F and Cl) have been generated through O₂‐oxidation of the corresponding alkyl radicals CHX₂^. in the gas phase. The IR spectroscopic characterization of both radicals in cryogenic Ar‐ and N₂‐matrices (15 K) is supported by ¹⁸O‐labeling and ab initio calculations at the UCCSD(T)/aug‐cc‐pVTZ level. Upon 266 nm laser irradiation, both radicals decompose mainly by releasing hydroxyl radicals (→HO^.+X₂CO) via the intermediacy of intriguing α‐hydroperoxyalkyl radicals (^.CX₂OOH), implying that the photooxidation of dihalogenated hydrocarbons might serve as important sources of HO^. radicals in the atmosphere.

链接：https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.201905858