Influence of Substituents on Haptotropic Rearrangements of Manganese(I)‐Phenalenide Complexes

Abstract Polycyclic Odd Alternant Hydrocarbons (POAHs) exhibit a characteristic electronic distribution that differs from that of even‐alternant hydrocarbons like naphthalene. We analyze how these electronic differences modify the bonding scenario and haptotropic migrations in complexes with POAH. Specifically, we examine manganese(I) complexes with mono‐functionalized phenalenide, varying both the position and nature of the substituent. We found that the prefered position of the substituent depends on the nature of the functional group. electron‐donor groups favor the position, while electron‐withdrawing prefer the position in the phenalenide. Contrary to naphthalene chromium complex, the Laplacian of the electron density, ρ ( r )), depicts the metal‐ligand interaction of these manganese(I)‐POAH complexes, consisting in position as charge donor atoms, and positions as charge acceptor atoms.