Initial and secondary intermediates in the reaction of OVCl3 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. 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 Cl2V(O)NH2 species, as well as to HCl arising from destruction of the complex. Identification of these species was supported by extensive 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 the computed frequencies. Similar experiments with (CH3)(3)N led, at best, to a very small degree of complex formation.