[5,6]‐Open Methanofullerene Derivatives of I_h‐C₈₀

Addition of S‐Heterocyclic Carbenes to Fullerenes: Formation and Characterization of Dithiomethano‐Bridged Derivatives

“…Such orientations of the Sc 3 N clusters have been reported commonly for the [6,6]-open and [5,6]-open methanobridged M 3 N@I h -C 80 (M=Sc, Y) structurally determined by X-ray crystallography. [16,18,22,23] By the comparison of the adducts with the vertical orientations of the Sc 3 N cluster, the [6,6]-adducts 14-I-V are energetically lower than the [5,6]-adducts 14-VIII-X. This result may support the experimentally observed predominant production of the [6,6]-open adducts although low yield formation of the [5,6]-open adducts cannot be excluded.…”

“…[e] Data from ref. [22]. Smartbeam mass spectrometer (Bruker Daltonics) with 1,1,4,4-tetraphenyl-1,3-butadiene (TPB) as the matrix in both positive and negative ion modes.…”

“…In particular, the E ox potentials of 13 and 14 are slightly lower than those of the related methanobridged Sc 3 N@I h -C 80 derivatives 15-19 (Figure 6). [19,21,22] It is also noteworthy that 12 and 14 exhibited slightly lower E ox 1 potentials than 11 and 13, respectively, suggesting that the energetically lower molecular orbitals of Ge -Ge bonds contribute more than those of SiÀ Si bonds. Previously, the similar slight cathodic shift of the E ox 1 potential has been reported for the digermirane adduct of Lu 3 N@I h -C 80 compared to the corresponding silicon analog.…”

Sc3N@Ih-C80 as a novel Lewis acid to trap abnormal N-heterocyclic carbenes: the unprecedented formation of a singly bonded [6,6,6]-adduct

“…3a ). 13 , 14 More surprisingly, the addition site on the cage of Sc 3 N@ I h -C 80 involves a triple hexagon junction (THJ) which is generally less reactive than the carbon atoms of other kinds on a fullerene cage. Such an addition pattern has never been observed or even expected for Sc 3 N@ I h -C 80 because previously reported singly bonded derivatives contained at least two substituents that are exclusively linked to the pentagon–hexagon–hexagon junction (PHHJ) carbon atoms unless the cage is severely functionalized.…”

Unexpected Formation of Metallofulleroids from Multicomponent Reactions, with Crystallographic and Computational Studies of the Cluster Motion

“…A subgroup of EMF, the nitride clusterfullerenes (NCFs), [13,14] especially the most abundant members M 3 N@I h -C 80 , have very high stability [15] that gives them high production yields, but meanwhile makes their chemical modification challenging. With notable exceptions, [16][17][18][19][20] most reactions of the NCFs with well-characterized derivatives are from cycloadditions, including the Bingel-Hirsch reaction, [21] Prato reaction, [22,23] Diels-Alder reaction, [24] diazo addition, [25,26] benzyne addition, [27,28] and reaction with azide [29] or ylide. [30] Overall, the pool of viable reactions on NCFs remains very limited; new reactions, and especially those not directly inspired from an analogous C 60 reaction, are still in strong demand.…”