Initial and secondary intermediates in the reactions of OVCl3 and CrCl2O2 with H2O have been characterized by matrix isolation infrared spectroscopy and density functional calculations. Twin jet co-deposition of these reagents led to a series of infrared absorptions that are assigned to the 1: 1 molecular complexes between these two species. Irradiation of these matrices with light of lambda > 300 nm led to complete destruction of the bands of complexes, and the growth of a number of new bands. These are assigned to the Cl2V(O)OH and ClCr(O)(2)OH species, as well as to HCl arising from destruction of the complex. Identification of these species was supported by isotopic labeling (O-18 and H-2), as well as by B3LYP/6-311G+(d,2p) and B3LYP/LANL2DZ density functional calculations. Good agreement was observed between the experimental and computed frequencies. The overall yield of product was low for these system, and was probably a consequence of the low basicity of H2O.