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Treatment of the open-cage fullerene C63H4NO2(Ph)2(Py)(N2C6H4) ( 1) with methanol at 150 °C results in an orifice-enlargement reaction to give C69H8NO(CO2Me)(Ph)(Py)(N2C6H4) ( 2). The overall yield from C60 to isolated 2 is 6.1 % (four steps). Compound 2 contains a 24-membered elliptic orifice that spans 8.45 Å along the major axis and 6.37 Å along the minor axis. The skeleton of 2 resembles the hypothetic C60H10 (5,5)-carbon nanotube endcap. The cup-shaped structure of 2 is able to include water, hydrogen cyanide, and acetylene, forming H2O@ 2, HCN@ 2, and C2H2@ 2, respectively. The molecular structures of H2O@ 2 and HCN@ 2 have been determined by X-ray crystallography. The 1H NMR spectra reveal substantial upfield shifts for the endohedral species, such as δ=−10.30 (for H2O), −2.74 and −14.26 (for C2H2), and −1.22 ppm (for HCN), owing to the strong shielding effects of the fullerene cage. [ABSTRACT FROM AUTHOR]

Reaction of C63NO2(Ph)2(Py) ( 1) with o-phenylenediamine and pyridine produces a mixture of C63H4NO2(Ph)2(Py)(N2C6H4) ( 2) and H2O@ 2. Compound 2 is a new open-cage fullerene containing a 20-membered heterocyclic orifice, which has been fully characterized by NMR spectroscopy, high-resolution mass spectrometry, and X-ray crystallography. The elliptical orifice of 2 spans 7.45 Å along the major axis and 5.62 Å along the minor axis, which is large enough to trap water and small organic molecules. Thus, heating a mixture of 2 and H2O@ 2 with hydrogen cyanide and formaldehyde in chlorobenzene affords HCN@ 2 and H2CO@ 2, respectively. The 1H NMR spectroscopy reveals substantial upfield shifts for the endohedral species ( δ=−1.30 to −11.30 ppm), owing to the strong shielding effect of the fullerene cage. [ABSTRACT FROM AUTHOR]

Analytically pure C60H18 is obtained by a Ru3 cluster complexation and decomplexation method. The crystal structure of C60H18 consists of one flattened hemisphere, to which all 18 hydrogen atoms are symmetrically bonded, and one curved hemisphere akin to C60. A benzenoid ring in the flattened hemisphere is isolated from the residual π systems by a belt composed of sp3-hybridized CH units. The average out-of-plane distances for carbon atoms attached to the benzenoid ring (0.14 Å) is substantially larger than that found in C60F18 (0.06 Å). Several long C(sp3)C(sp3) single bond lengths [1.61(3)-1.65(3) Å] are observed for C60H18. The reaction of [Ru3(CO)12] and C60H18 produces [Ru3(CO)9(μ3-η2,η2,η2-C60H18)] ( 1), where the Ru3 triangle is regiospecifically linked to the hexagon opposite to the benzenoid ring. Compound 1 is the first transition metal complex of a polyhydrofullerene (fullerane). C60H18 and 1 have been characterized by 1H and 13C NMR, UV/Vis, and mass spectroscopies. The HOMO-LUMO gap of C60H18 is evaluated to be 1.51 V by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Ligand substitution reaction of the fullerophosphine PPh 2 ( o -C 6 H 4 )(CH 2 NMeCH)C 60 ( 1 ) with AuCl(SC 4 H 8 ) affords AuCl(PPh 2 ( o -C 6 H 4 )(CH 2 NMeCH)C 60 ) ( 2 ) in good yields. In the presence of AgPF 6 , compound 2 reacts with 1 to produce [Au(PPh 2 ( o -C 6 H 4 )(CH 2 NMeCH)C 60 ) 2 ]PF 6 ( 3 ), where the Au(I) ion is coordinated by two molecules of 1 in a dumbbell-shaped feature. On the other hand, compound 1 undergoes a nucleophilic addition to (AuC CPh) n to generate Au(C CPh)(PPh 2 ( o -C 6 H 4 )(CH 2 NMeCH)C 60 ) ( 4 ). The structures of 2 – 4 have been determined by an X-ray diffraction study. [ABSTRACT FROM AUTHOR]

Abstract: Reaction of the pentamethylhydrofullerene C60HMe5 (1) with Ru3(CO)12 in refluxing toluene affords the face-capping cluster complex Ru3(CO)9(η 2,η 2,η 2-C60HMe5) (2). Elution of 1 on TLC plates (silica gel) leads to hydroxyepoxidation of the cyclopentadiene group to generate C60Me5(O)(OH) (3) and C60Me5(O)2(OH) (4). Reaction of 3 with Ru3(CO)12 in refluxing toluene gives the face-capping complex Ru3(CO)9(η 2,η 2,η 2-C60Me5(O)(OH)) (5). The structures of 2, 3, and 5 have been determined by a single-crystal X-ray diffraction study. [Copyright &y& Elsevier]

Reactions of the open-cage fullerene C63NO2(Py)(Ph)2 ( 1) with [Ru3(CO)12] produce [Ru3(CO)8(μ,η5-C63NO2(Py)(Ph)2)] ( 2), [Ru2H(CO)3(μ,η7-C63N(Py)(Ph)(C6H4))] ( 3), and [Ru(CO)(Py)2(η3-C63NO2(Py)(Ph)2)] ( 4), in which the orifice sizes are modified from 12 to 8, 11, and 15-membered ring, through ruthenium-mediated CO and CC bond activation and formation. [ABSTRACT FROM AUTHOR]