Formation and Infrared Spectrum of the Open-Form 2-Bromoethyl Radical (2-C2H4Br•) from Ultraviolet Irradiation of a C2H4/Br2/p-H2 Matrix

The addition reaction of halogens to alkenes is important in organic synthesis, but the reaction intermediate has rarely been detected. Whether the structure of the intermediate bromoethyl (C2H4Br center dot) radical is a bridged form or an open form is unclear. We took advantage of the diminished cage effect of solid p-H-2 and employed infrared (IR) absorption to record the IR spectrum of C2H4Br center dot after photolysis of a C2H4/Br-2/p-H-2 matrix at 254 nm, followed by annealing. New spectral features at 676.9, 776.7, 1068.5, 1148.0, 3041.8, and 3126.8 cm(-1) are assigned to the open-form 2-bromoethyl radical, according to their photolytic behavior and comparison with scaled harmonic vibrational wavenumbers and IR intensities calculated with the B2PLYPD3/6-311++G(2df,2p) method.

Automated summary

The addition reaction of halogens to alkenes is crucial in organic synthesis, with the structure of the intermediate bromoethyl radical, whether it is bridged or open form, being unclear. Researchers successfully recorded and analyzed the IR spectrum of the bromoethyl radical intermediate using the diminished cage effect of solid p-H-2 and IR absorption technique.