Fulleride-metal η⁵ sandwich and multi-decker sandwich complexes: A DFT prediction

The (C₆₀ CN)^- formed by the reaction of CN^- with fullerene shows high electron rich character, very similar to C₆₀ ˙^- , and it behaves as a large anion. Similar to Cp^- , the bulky anion, (C₆₀ CN)^- , acts as a strong η⁵ ligand towards transition metal centers. Previous studies on η⁵ coordination of fullerene cage are reported for pseudo fullerenes whereas the present study deals with sandwich complexes of (C₆₀ CN)^- with Fe(II), Ru(II), Cr(II), Mo(II), and Ni(II) and multi-decker sandwich complexes of CN-fullerides with Fe(II). The structural parameters of these complexes and the corresponding Cp^- complexes showed very close resemblance. Analysis of the metal-to-carbon bonding molecular orbitals showed that sandwich complex [Fe(η⁵ -(C₆₀ CN)^- )₂ ] exhibit bonding features very similar to that of ferrocene. Also, a 6-fold decrease in the band gap energy is observed for [Fe(η⁵ -(C₆₀ CN)^- )₂ ] compared to ferrocene. The energy of dissociation (ΔE) of the ligand (C₆₀ CN)^- from [Fe(η⁵ -(C₆₀ CN)^- )₂ ] is slightly lower than the ΔE of a Cp* ligand from a ferrocene derivative wherein each cyclopentadienyl unit is substituted with four tertiary butyl groups. The (C₆₀ CN)^- ligand behaved as one of the bulkiest ligands in the chemistry of sandwich complexes. Further, the coordinating ability of the dianion, (C₆₀ (CN)₂ )^2- is evaluated which showed strong coordination ability simultaneously with two metal centers leading to the formation of multi-decker sandwich and pearl-necklace type polymeric structures.