Ammonia Activation by Early Transition Metal Atoms (Sc, Ti, and V). Matrix Isolation Infrared Spectroscopic and Density Functional Theory Studies
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Abstract
Reactions of the early transition metal atoms Sc, Ti, and V with NH3 molecules in solid argon matrix have been studied by infrared spectroscopy and density functional calculations. It is found that the ground-state metal atoms reacted with NH3 to form the MNH3 (M = Sc, Ti, and V) complexes spontaneously on annealing. The MNH3 complexes underwent photochemical rearrangement to the HMNH2 molecules. The HScNH2 molecule further decomposed to ScNH + H2 upon ultraviolet−visible irradiation. While in the Ti + NH3 and V + NH3 reaction systems, the novel H2TiNH and H2VNH species were the ultimate products generated from the photoinduced isomerization of the HTiNH2 and HVNH2 intermediates. All the reaction intermediates and products have been identified by isotopic substitutions and by density functional theoretical frequency calculations. Qualitative analysis of the possible reaction paths for these reactions is given, including various minima and transition states. The results have been compared with previous works covering middle transition metal atoms as well as main group atom reactions with NH3 to obtain periodic trends for these reactions.
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