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Transition Metal Complex Formation

“…This was confirmed in some theoretical calculations [5][6][7][8]. This was confirmed in some theoretical calculations [5][6][7][8].…”

“…Various single-crystal structures and spectroscopic studies show that the complexation of transition metals to the fullerene core proceeds similar to wellestablished reactions of electron-deficient olefins in a dihapto manner to one or more π-bonds or as hydrometalation reactions. This was confirmed in some theoretical calculations [5][6][7][8]. The resulting thermodynamic control explains the remarkable regioselectivity observed at the formation of higher addition products, for example bisadducts or hexakisadducts.…”

“…As expected they react more like a cyclohexatriene unit, as shown by C 60 's ability to bind to various cluster frameworks via a face-capping bonding mode to give µ 3 -η 2 :η 2 :η 2 -C 60 -complexes (Figure 7.5). The metal-carbon bonds in Ru 3 (CO) 9 (µ 3η 2 :η 2 :η 2 -C 60 ) are therefore stronger than in Ru 3 (CO) 9 (µ 3 -η 2 :η 2 :η 2 -C 6 H 6 ) [7]. Thus sufficient overlap with one η 6 -bound metal is not given but the overlap of π-orbitals with the metaltriangle of the metal-cluster shown in Figure 7.5 can be very effective.…”

“…This is one more indication for the low aromaticity of the C 60 hexagons. Molecular orbital calculations on the complex of Ru 3 (CO) 9 [7] with either C 60 or benzene showed that, compared with the corresponding binding of a cluster fragment to benzene, C 60 can bind via many more fragment orbitals, allowing the fullerene to form many more bonding interactions. Owing to the curvature of C 60 the exohedral π-orbitals are oriented about 10°a way from the perpendicular to the face of the C 6 -ring [66].…”

Cyclic voltammetry modeling, geometries, and electronic properties for metallofullerene complexes with μ3‐η2:η2:η2‐C60 bonding mode

“…In particular, the electrochemistry of fullerenes has been one of the most intensely studied aspects of fullerene chemistry 17–23. Various metal cluster‐C 60 exohedral metallofullerene complexes24–34 have been investigated to understand the effects of metal cluster coordination on the chemical and physical properties of C 60 , reactivities and electrochemical properties of these complexes, and ultimately to develop new electronic nanomaterials and nanodevices 35. The metal cluster‐C 60 complexes have been dominated by a π‐type metal cluster‐C 60 interaction with the μ 3 ‐η 2 :η 2 :η 2 ‐C 60 bonding mode 25–35.…”