AbstractOn the way to the fullerene‐acetylene hybrid carbon allotropes2and6, the oxidative homocoupling of the 2‐functionalized 1‐ethynylated C60derivatives11, 12, 14, and15was investigated. UnderGlaser‐Hayconditions, the two soluble dumbbell‐shaped bisfullerenes17and18, with two C60moieties linked by a buta‐1,3‐diynediyl bridge, were formed in 52 and 82% yield, respectively (Scheme 2). Cyclic‐voltammetric measurements revealed that there is no significant electronic communication between the two fullerene spheresviathe buta‐1,3‐diynediyl linker. Removal of the 3,4,5,6‐tetrahydro‐2H‐pyran‐2‐yl (Thp) protecting groups in18gave in 80% yield the highly insoluble dumbbell19with methanol groups in the 2,2′‐positions of the buta‐1,3‐diynediyl‐bridged carbon spheres. Attempted conversion of19to the all‐carbon dianion6(C 1242−)viabase‐induced elimination of formaldehyde was not successful presumably due toexo‐dig cyclization of the formed alkoxides. The occurrence of this cyclization under furan formation was proven for 2‐[4‐(trimethylsilyl)buta‐1,3‐diyn‐1‐yl][60]fullerene‐1‐methanol (21), a soluble model compound for19(Scheme 3). To compare the properties of ethynylated fullerene mono‐adducts to those of corresponding higher adducts, hexakis‐adducts26and28with an octahedral functionalization pattern resulting from all‐e (equatorial) additions were prepared by the reversible‐template method ofHirsch (Scheme 4). Reaction of the ethynylated mono‐adducts25or13with diethyl 2‐bromomalonate/1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in the presence of 1,9‐dimethylanthracene (DMA) as reversible template led to26and28in 28 and 22% yield, respectively. Preliminary experiments indicated a significant change in reactivity and NMR spe