Initial and secondary intermediates in the reaction of CrCl2O2 with NH3 have been characterized by matrix isolation infrared spectroscopy and density functional calculations. Twin-jet co-deposition of these two reagents led to a series of infrared absorptions that are assigned to the 1:1 molecular complex between these two species. The shift of v(2) of NH3 in the complex was +218 cm(-1), indicating that CrCl2O2 is a moderately strong Lewis acid. Irradiation of these matrices with light of lambda > 300 nm led to complete destruction of the complex and the growth of a number of new bands. These are assigned to the ClCr(O)(2)NH2 species, as well as to HCl arising from destruction of the complex. Identification of these species was supported by isotopic labeling, (N-15 and H-2), as well as by B3LYP/6-311G+(2d,3p) density functional calculations. Good agreement was observed between the experimental and computed frequencies.