Theoretical study of structures and reactivities of the complexes of metals in the zero-valent state with fullerene ligands

Abstract

Possible reaction routes of dimerization of intermediate fullerene-containing zero-valent metal complexes probably formed by the reduction of the phosphine-containing Co^II and Ni^II complexes in the presence of C₆₀ were analyzed using the density functional theory with the PBE functional. The found energetic effects of the formation of the binuclear complexes with different structures, including those containing the dimer of fullerene C₁₂₀ performing a bridging function, together with the estimated energy barriers to the symmetry-forbidden 2+2 cycloaddition in the coordination sphere are crucial in the understanding of the structures of the observed reaction products.