Matrix isolation investigation of the photochemical reaction of methyl-substituted benzenes with CrCl2O2.
The matrix isolation technique, combined with infrared spectroscopy, has been used to characterize the products of the photochemical reactions of toluene, m-, o-, and p-xylene, mesitylene, and hexamethylbenzene with CrCl2O2. While initial twin jet deposition of the reagents led to no visible changes in the recorded spectra, strong product bands were noted following irradiation with light of lambda > 300 nm. The irradiation was shown to lead to oxygen atom transfer, forming complexes between methylcyclohexadienone derivatives and CrCl2O. With the xylenes and mesitylene, di- and trimethylphenols, complexed to CrCl2O, were also observed, respectively. This latter result arises from C-H bond activation and oxygen atom insertion into a C-H bond. The identification of the complexes was further supported by isotopic labeling (2H) and by density functional calculations at the B3LYP/6-311G++(d,2p) level. Product distributions were rationalized by an analysis of the electron density distribution.
Hoops
Michael D
MD
Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, Ohio 45221-0172, USA.
Ault
Bruce S
BS