We report the details of our study to synthesize a new endohedral fullerene, H2@C60, in more than 100 mg quantities by closure of the 13-membered ring orifice of an open-cage fullerene using four-step organic reactions. The 13-membered ring orifice in a previously synthesized open-cage fullerene incorporating hydrogen in 100% yield was reduced to a 12-membered ring by extrusion of a sulfur atom at the rim of the orifice, and the ring was further reduced into an eight-membered ring by reductive coupling of two carbonyl groups also at the orifice. Final closure of the orifice was completed by a thermal reaction. Purification of H2@C60 was accomplished by recycle HPLC. A gradual downfield shift of the NMR signal for the encapsulated hydrogen observed upon reduction of the orifice size was interpreted based on the gauge-independent atomic orbital (GIAO) and the nucleus-independent chemical shift (NICS) calculations. The spectral as well as electrochemical examination of the properties of H2@C60 has shown that the electronic interaction between the encapsulated hydrogen and outer C60 pi-system is quite small but becomes appreciable when the outer pi-system acquires more than three extra electrons. Four kinds of exohedral derivatives of H2@C60 were synthesized. The tendency in the shift of the NMR signal of the inner hydrogen was found to be quite similar to that observed for the 3He NMR signal of the corresponding derivatives of 3He@C60.