A stabilization rule for metal carbido cluster bearing μ3-carbido single-atom-ligand encapsulated in carbon cage

Metal carbido complexes bearing single-carbon-atom ligand such as nitrogenase provide ideal models of adsorbed carbon atoms in heterogeneous catalysis. Trimetallic μ 3 -carbido clusterfullerenes found recently represent the simplest metal carbido complexes with the ligands being only carbon atoms, but only few are crystallographically characterized, and its formation prerequisite is unclear. Herein, we synthesize and isolate three vanadium-based μ 3 -CCFs featuring V = C double bonds and high valence state of V (+4), including VSc 2 C@ I h (7)-C 80 , VSc 2 C@ D 5 h (6)-C 80 and VSc 2 C@ D 3 h (5)-C 78 . Based on a systematic theoretical study of all reported μ 3 -carbido clusterfullerenes, we further propose a supplemental Octet Rule, i.e., an eight-electron configuration of the μ 3 -carbido ligand is needed for stabilization of metal carbido clusters within μ 3 -carbido clusterfullerenes. Distinct from the classic Effective Atomic Number rule based on valence electron count of metal proposed in the 1920s, this rule counts the valence electrons of the single-carbon-atom ligand, and offers a general rule governing the stabilities of μ 3 -carbido clusterfullerenes. Trimetallic carbido clusterfullerenes (CCFs) represent the simplest metal carbido complexes with the ligands being only carbon atoms, but the formation prerequisite is unclear. Herein, the authors report the syntheses of three novel vanadium(V)-based CCFs featuring high vanadium valence state and propose a supplemental Octet Rule