Abstract
Metals can interact with carbon cages in the following ways: (1) stable carbon cages (i.e., fullerenes) function as electronegative olefins in their exohedral η2 bonding to transition metals; (2) endohedral metallofullerenes with a highly electropositive lanthanide (Ln) inside the carbon cage can be considered to be ionic with lanthanide cations, Ln3+, and fullerene anions; (3) fullerenes too small for independent existence can be stabilized by internal covalent bonding to an endohedral metal atom using the central carbon atoms of pentagon triplets,i.e triquinacene, units, in complexes such as M@C28 (M=Ti, Zr, Hf, and U), derived from the tetrahedral fullerene C28; (4) metal atoms can occur as vertices of binary mixed metal-carbon cages in both early transition metal complexes of the types M14C13, M8C12, and M13C22 (e.g., M=Ti) and copper-carbon cages of the types Cu2n +1C2n + (n≤10), Cu7C8 +, Cu9C10 + and Cu12C12 +. The presence of metal atoms as vertices of carbon cages changes radically their stoichiometries and thus their structures. Thus, early transition metals form cages such as Ti14C13 assumed to have titanium atoms at the vertices and face midpoints of a 3×3×3 cube and carbon atoms at the edge midpoints and center of the cube and Ti13C22 assumed to have titanium atoms at the edge midpoints and center of a 3×3×3 cube as well as C2 units and carbon atoms at the vertices and face midpoints, respectively, of the cube. Elimination of the face metal atoms from the Ti14C13 structure as well as the center carbon atom, which has been achieved experimentally by photofragmentation, leads to the Ti8C12 cluster. The structure of this cluster is based on a tetracapped tetrahedron withT d symmetry with two distinct quartets of titanium atoms, six distinct C2 pairs, and 36 direct Ti−C interactions. The copper-carbon cages of various stoichiometries are suggested to have prismatic, antiprismatic, or cuboctahedral structures in which the electronic configurations of the copper atoms approach the favored 18-electron rare gas configuration.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 862–869, May, 1998.
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King, R.B. Topological aspects of metals in carbon cages: Analogies with organometallic chemistry. Russ Chem Bull 47, 833–840 (1998). https://doi.org/10.1007/BF02498149
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DOI: https://doi.org/10.1007/BF02498149