The matrix isolation technique, combined with infrared spectroscopy and theoretical calculations, has been used to characterize the products of the photochemical reactions of aniline, anisole, and N,N-dimethylaniline with CrCl 2 O 2 . While initial twin jet deposition of the reagents did not lead to product formation, new bands were noted following irradiation with light of λ>300nm. In the reactions of CrCl 2 O 2 and aniline, irradiation led to HCl formation, very likely accompanied by CrClO 2 (H)NC 6 H 5 formation, and a mixture of isomers of CrCl 2 O-aminocyclohexa-2,4-dienone via oxygen atom transfer. CrCl 2 O 2 and aniline were also codeposited as cryogenic thin films, producing new bands. Irradiation of these films led to further growth of these bands. The same products were identified in the thin film studies as were observed in the argon matrix experiments. The irradiation of the matrices containing CrCl 2 O 2 and anisole and N,N-dimethylaniline were shown to lead to oxygen atom transfer, forming complexes between the corresponding cyclic ketone derivatives and CrCl 2 O. The identification of the complexes were supported by density functional calculations at the B3LYP/6-311G++(d,2p) level and isotopic labeling (in the case of aniline).