Matrix isolation study of the photochemical reaction of cyclohexane and cyclohexene with CrCl2O2

✍ Scribed by Michael D. Hoops; Bruce S. Ault

• Publisher: Elsevier Science
• Year: 2007
• Tongue: English
• Weight: 476 KB
• Volume: 826
• Category: Article
• ISSN: 0022-2860
• DOI: 10.1016/j.molstruc.2006.04.017

✦ Synopsis

The matrix isolation technique, combined with infrared spectroscopy, has been used to characterize the products of the photochemical reactions of cyclohexane and cyclohexene with CrCl 2 O 2 . 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 k > 300 nm. The irradiation was shown to lead to oxygen atom transfer, forming complexes between cyclic alcohol derivatives and CrCl 2 O, although complexes between ring expansion products and CrCl 2 O could not be ruled out. This latter result could arise from C-C bond activation and oxygen atom insertion into a C-C bond. For the cyclohexene system, the cyclohexanone-CrCl 2 O complex was also observed. The identification of the complexes was further supported by isotopic labeling ( 2 H) and by density functional calculations at the B3LYP/6-311G++(d,2p) level.