Energetic and topological analysis of the reaction of Mo and Mo2 with NH3, C2H2, and C2H4 molecules

The Density functional theory has been applied to characterize the structural features of Mo1,2NH3,C2H4, and C2H2 compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo1,2NH3), the interaction between Mo (or Mo2) and C2H4 (or C2H2) are the low‐spin (MoC2H4 and C2H2) and high‐spin (Mo2C2H4 and C2H2) complexes. In the ground state of Mo1,2C2H4 and C2H2, the metal‐center always reacts with the CC center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a π‐acceptor ligand correlates with a maximum charge transfer from the metal center to the CC bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the CC basin. The interaction between Mo1,2 and C2H4 (or C2H2) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo1,2 and NH3, and the partners are bound by an electrostatic interaction. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1647–1655, 2004

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