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

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.