Initial and secondary intermediates in the reaction of VCl4 with NH3 have been characterized by matrix isolation infrared spectroscopy and density functional calculations. Twin jet codeposition of these two reagents led to a series of moderately intense infrared absorptions that have been 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 have been assigned to the Cl3VNH2 species, complexed with a single HCl arising from destruction of the complex. Identification of these species (1:1 complex and photoproduct) was supported by extensive isotopic labeling (N-15 and H-2), as well as by B3LYP/6-311++g(d, 2p) density functional calculations. Good agreement was observed between the experimental and computed frequencies. The binding energy of the 1:1 complex was calculated to be DeltaE(298)degrees = -11.43 kcal/mol at this level of theory. Similar experiments with (CH3)(3)N led to no detectable products.