Laser-ablated tantalum atoms react with ammonia to form the metal-ammonia complexes Ta(NH3) and Ta(NH3)(2) spontaneously on annealing. These complexes underwent photochemical rearrangement to form the imido molecule H2TaNH and amido complex H2Ta(NH2)(2). The reaction products have been identified by isotopic substitutions as well as density functional theoretical frequency calculations. In addition, reaction mechanism of the possible reaction paths for these reactions is discussed. (C) 2011 Elsevier B.V. All rights reserved.