Addition Reaction of Fe(CO)n (n=3∼5) on Fullerene C50, C60, and C70: A Density Functional Theory Study

The electronic structure and reactivities of Fe(CO)(n) (n = 3 similar to 5) addition to different fullerenes have been investigated through the first-principles calculations, and the results indicate that Fe(CO)(3) and Fe(CO)(4) can be adsorbed to the outside network of fullerene via hollow and bridge sites, respectively. Both of them have larger binding energy, but when Fe(CO)(5) is adsorbed via the top site, the binding energy is relatively smaller. According to the directional curvature theory, the reactivities of Fe(CO)(3) addition to the fullerenes are determined by KM of the ring center, and those of Fe(CO)(4) addition by KD of the C-C bond curvature; while for Fe(CO)(5), it presents weak reactivities in the addition reaction because of the larger volume effect. No matter whether the addition reaction takes place on the hollow or bridge site, the binding energies show a linear relationship with KD. This work further enriched the directional curvature theory and applied the isolobel analogy theory in the fullerene addition reactions.