Electric deflection experiments have been performed on metal-benzene compounds (for scandium, vanadium, nickel, niobium, and tantalum). CASSCF + MRCI calculations are reported for Sc, V, and Ni complexes. The lowest energy structures correspond to long-range states (distance between the metal atom and the center of the benzene molecule superior to 4 Angstrom), while the short-range states are metastable against dissociation. The comparison between experimental results and theory demonstrates the importance of these long-range states.