DFT studies have been carried out to investigate the role of nitrogen participation in the interring haptotropic rearrangements of [(η⁶-C₆H₅)(C₆H₄-4-NH₂)]Cr(CO)₃ and [(η⁶-C₆H₅)(C₆H₄-2-NH₂)]Cr(CO)₃. For the para-substituted case, where intramolecular coordination of nitrogen to chromium is not possible, DFT modeling predicts an activation barrier of 32.5 kcal mol⁻¹, which is in very close agreement with the experimentally determined value of 32.57 kcal mol⁻¹. In the case of the ortho-substituted isomers, modeling of a mechanism that does not invoke stabilization via nitrogen coordination yields a predicted energy barrier of 32.7 kcal mol⁻¹, while a mechanism that does invoke nitrogen participation and accounts for interconversion of rotational isomers gives a predicted value of 30.2 kcal mol⁻¹. This is consistent with the experimentally determined value of 31.22 kcal mol⁻¹. These data provide evidence that intramolecular stabilization via nitrogen coordination to chromium is responsible for the ortho substituted isomer undergoing haptotropic rearrangement with a rate nearly five times greater than that observed for the para isomer. For the mechanism that invokes ortho-amino group participation, transition state analysis in the frame of Bader theory shows that each transition state along the proposed mechanistic pathway has a bond critical point between nitrogen and chromium.