Self-driven carbon atom implantation into fullerene embedding metal–carbon cluster

Hundreds of members have been synthesized and versatile applications have been promised for endofullerenes (EFs) in the past 30 y. However, the formation mechanism of EFs is still a long-standing puzzle to chemists, especially the mechanism of embedding clusters into charged carbon cages. Here, based on synthesis and structures of two representative vanadium–scandium–carbido/carbide EFs, VSc(2)C@I(h) (7)-C(80) and VSc(2)C(2)@I(h) (7)-C(80), a reasonable mechanism—C(1) implantation (a carbon atom is implanted into carbon cage)—is proposed to interpret the evolution from VSc(2)C carbido to VSc(2)C(2) carbide cluster. Supported by theoretical calculations together with crystallographic characterization, the single electron on vanadium (V) in VSc(2)C@I(h) (7)-C(80) is proved to facilitate the C(1) implantation. While the V=C double bond is identified for VSc(2)C@I(h) (7)-C(80), after C(1) implantation the distance between V and C atoms in VSc(2)C(2)@I(h) (7)-C(80) falls into the range of single bond lengths as previously shown in typical V-based organometallic complexes. This work exemplifies in situ self-driven implantation of an outer carbon atom into a charged carbon cage, which is different from previous heterogeneous implantation of nonmetal atoms (Group-V or -VIII atoms) driven by high-energy ion bombardment or high-pressure offline, and the proposed C(1) implantation mechanism represents a heretofore unknown metal–carbon cluster encapsulation mechanism and can be the fundamental basis for EF family genesis.