A haptotropic rearrangement in an organometallic compound involves the movement of a metal fragment, such as chromium tricarbonyl, between two different pi-coordinating groups of a ligand, such as the aromatic rings of a fluorenyl, naphthyl, or biphenyl ligand. These rearrangements have attracted attention recently for their potential application as molecular switches, especially when the rearrangement can be thermally or photochemically reversed. Previous studies have suggested that migration of chromium tricarbonyl between the aromatic rings of a substituted biphenyl ligand will not occur when steric hindrance forces the phenyl-phenyl dihedral angle to be greater than 22º. This implies the necessity for co-planarity of phenyl rings during haptotropic rearrangement. We have shown that when a strong electron donor, such as an amino group, is attached to the non-coordinated ring of (eta-6)-(2-aminobiphenyl) chromium tricarbonyl, a migration of the metal fragment is observed, even though the phenyl-phenyl dihedral angle is 58º. To examine this rearrangement, we have developed syntheses for both isomers of (eta-6)-(2-aminobiphenyl) chromium tricarbonyl, and have shown that the compound with the amino substituent attached to the coordinated ring is the thermodynamically more stable isomer. We report single crystal X-ray diffraction studies for both compounds, showing that the thermodynamically less stable isomer has a 58º phenyl-phenyl dihedral angle, consistent with our DFT studies. Heating this compound effects a rearrangement to the thermodynamically more stable isomer, with a half-life of 41 minutes at 140 ºC.