Characterization of Alkoxycarbonyl Radicals by Step‐Scan Time‐Resolved Infrared Spectroscopy

A series of alkoxycarbonyl radicals has been generated by laser flash photolysis (355 nm) of fluorenone oxime alkyl oxalates in carbon tetrachloride and characterized by time‐resolved infrared spectroscopy using the step‐scan technique. The alkoxycarbonyl radicals ( $\tilde {\nu}$ C=O = 1802 cm −1 for R = ethyl) generally have a lifetime of several microseconds, decaying by reaction with the solvent to yield esters of chloroformic acid. In some cases, decarboxylation yielding alkyl radicals has also been observed. Thus, photolysis of fluorenone oxime tert ‐butyl oxalate results in the formation of tert ‐butoxycarbonyl radicals, which subsequently decay, mainly yielding CO 2 and tert ‐butyl radicals. The benzyloxycarbonyl radical and the acetoneiminoxycarbonyl radical both decarboxylate too rapidly to be detected with our spectrometer (25 ns rise‐time). Upon purging the solution with oxygen, the alkoxycarbonyl radicals were efficiently quenched, to yield alkoxycarbonylperoxy radicals ( $\tilde {\nu}$ C=O = 1845 cm −1 for R = ethyl), which again had a lifetime of the order of several microseconds. A short‐lived transient ( $\tilde {\nu}$ = 1768 cm −1 , τ ≈ 200 ns) is assigned as the carbonyloxy radical 4a on the basis of comparison with time‐resolved UV/Vis data. A further product of the photolysis of fluorenone oxime oxalates can be tentatively assigned as the 9‐fluorenylideneiminoxy radical 3 ( $\tilde {\nu}$ = 1670 cm −1 ), which according to our DFT calculations should show a very intense $\tilde {\nu}$ C=N−O,as. = 1665 cm −1 . Fluorenone oxime oxalates are compounds well suited as precursors for alkoxycarbonyl radicals, since they are easily synthesized as crystalline solids, show a convenient absorption at λ = 355 nm, and exhibit a high degree of thermal stability.