Endohedral Hydrogen Fullerene - Organic Synthesis

Organic Synthesis

Scheme 1 presents an overview of the first step, the creation of a 13 membered ring orifice on the fullerene surface. A 1,2,4-triazine 2 is fitted with two phenyl groups and a pyridine group for reasons of solubility and reacted in 1,2-dichlorobenzene with pristine C₆₀ fullerene 2 in a Diels-Alder reaction at high temperature and for an extended reaction time. In this reaction nitrogen is expulsed and an 8-membered ring is formed (3). This orifice is further extended by reaction with singlet oxygen in carbon tetrachloride which causes one of the ring alkene groups to oxidize to a ketone. The 12-ring is extended to a 13-ring by reaction with elemental sulfur in presence of tetrakis(dimethylamino)ethylene.

The proposed reaction mechanism is depicted in a plat surface rendition in scheme 2. In the first step the triazine reacts with the fullerene in a Diels-Alder reaction. In the second step nitrogen is expulsed from the DA adduct 2 resulting in the formation of a fused aza-cyclohexadiene ring followed by a cycloaddition to an intermediate 4 with two cyclopropane rings. This intermediate quickly rearranges in a retro cycloaddition to the 8 membered ring product 5. In silico calculations show that the electrons in the HOMO reside primarily in the double bonds of the butadiene part of the ring and indeed singlet oxygen reacts at these positions through the dioxetane intermediate 6 with alkene cleavage to diketone 7 (only one isomer shown). Elemental sulfur S₈ is inserted into the single bond of the diene group leading to the extension of the ring to 13 atoms (structures 8 and 9 are identical). Tetrakis(dimethylamino)ethylene activates this bond for electrophilic sulfur addition either by one-electron reduction or by complexation.

From X-ray crystallography it is determined that the shape of the orifice in the sulfur compound is roughly a circle. Inserting hydrogen in this compound is an easy step taking place with 100% efficiency. Zipping up the orifice is a reversal of the steps required to open the cage. Care must be taken to keep the reaction conditions below 160 °C on order to prevent hydrogen from escaping. m-CPBA oxidizes the sulfur group to a sulfoxide group which can then be extracted from the ring by a photochemical reaction under visible light in toluene. The two ketone groups are re-coupled in a McMurry reaction with titanium tetrachloride and elemental zinc. The reverse cycloadditions take place at 340 °C in a vacuum splitting of 2-cyanopyridine and diphenylacetylene resulting in the formation of H₂@C₆₀ at a 40% chemical yield starting from pristine fullerene.