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Infrared spectra of the chloromethyl and bromomethyl cations in solid argon
Renhu Ma1, Mohua Chen, Mingfei Zhou
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Advanced Materials Laboratory, Fudan University, Shanghai 200433, Pr China.
Abstract:
Infrared spectra of chloromethyl and bromomethyl cations isolated in solid argon are reported. Cocondensation of dichloromethane and dibromomethane with high-frequency discharged argon at 4 K produces the dichloromethane and dibromomethane cations, which dissociate upon visible light irradiation to form the chloromethyl and bromomethyl cations. On the basis of isotopic substitutions ((13)C and deuterium) as well as theoretical frequency calculations, photosensitive absorptions are assigned to different vibrational modes of the chloromethyl and bromomethyl cations. Theoretical calculations predict that the halomethyl cations have a planar C(2v) symmetry with a shorter C-X bond and longer C-H bonds relative to those of the halomethyl free radicals.
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