Theoretical Study of Two-State Reactivity of Transition Metal Cations: The “Difficult” Case of Iron Ion Interacting with Water, Ammonia, and Methane

Abstract

The potential energy surfaces corresponding to the dehydrogenation reaction of H2O, NH3, and CH4 molecules by Fe+(6D, 4F) cation have been investigated in the framework of the density functional theory in its B3LYP formulation and employing a new optimized basis set for iron. In all cases, the low-spin ion−dipole complex, which is the most stable species on the respective potential energy hypersurfaces, is initially formed. In the second step, a hydrogen shift process leads to the formation of the insertion products, which are more stable in a low-spin state. From these intermediates, three dissociation channels have been considered. All of the results have been compared with existing experimental and theoretical data. Results show that the three insertion pathways are significantly different, although spin crossings between high- and low-spin surfaces are observed in all cases. The topological analysis of the electron localization function has been used to characterize the nature of the bonds for all of the minima and transition states along the paths.