Methoxychlorocarbene. Matrix Spectroscopy and Photochemistry

Article abstract of DOI:10.1021/ja00261a017

Irradiation of 3-chloro-3-methoxydiazirine matrix isolated in argon or nitrogen at 10 K gives methoxychlorocarbene.The carbene was observed by IR and UV spectroscopy.Deuterium and 18O labeling indicated significant C-O double bond character in the carbene, which was exhibited in an intense IR absorption at ca. 1300 cm^-1.The time evolution and wavelength dependence of the IR bands indicate two geometric isomers for the carbene, with distinct IR absorptions.The cis-carbene shows a significantly lower energy C-Cl stretch than the trans, consistent with an anomeric interaction.Irradiation of the carbene gives acetyl chloride, ketene, and HCl in argon matrices.In nitrogen, small amounts of CO and methylchloride are also observed.Several mechanisms are proposed to explain the photochemical results.