Search

Condensation of the formyl group of Cp3Fe4(CO)4(C5H4CHO) with N-methylglycine and C60 produces Cp3Fe4(CO)4(C5H4-CHNMeCH2C60) (1), where one cyclopentadienyl ring of the tetrairon cluster is linked to a fulleropyrrolidinyl moiety. A similar reaction with the bisformyl cluster Cp2Fe4(CO)4(C5H4CHO)2 affords Cp2Fe4(CO)4(C5H4-CHNMeCH2C60)2 (2). Compounds 1 and 2 have been characterized by mass, IR, UV-Vis, and NMR spectroscopy. The electrochemistry of 1 and 2 was investigated by cyclic voltammetry and differential pulse voltammetry.

Reaction of PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60) (1) and (μ-H)(3)Re(3)(CO)(11)(NCMe) in refluxing chlorobenzene affords the monorhenium complex HRe(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (2), and the dirhenium complexes (μ-H)Re(2)(CO)(7)(μ,η(3)-PPh(o-C(6)H(4))(2)(CH(2)NMeCH)C(60)) (3) and (μ-H)Re(2)(CO)(5)(μ-SSOH)(μ,η(5)-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. The oxatrisulfanyl (-SSOH) ligand of 4 likely arises from decomposition of CS(2) on silica gel during the purification processes.

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]

Fullerene adducts, open-cage fullerenes, and endohedral fullerenes represent the fundamental research topics of modified fullerenes. Recently, attachment of metal fragments to the fullerene cages, and investigating their properties and reactivity, becomes an important area within fullerene chemistry. This article provides a brief review of some selected recent advances in organometallic reactions of modified fullerenes with a focus on the work in the author's group. [ABSTRACT FROM AUTHOR]

The reactions of [(μ-H)3Re3(CO)11(NCMe)] with Sc2@C82- C3 v(8), Sc2C2@C80- C2 v(5), Sc2O@C82- Cs(6), C86- C2(17), and C86- Cs(16) have been carried out to produce face-capping cluster complexes. The Re3 triangles are found to bind to the sumanene-type hexagons on the fullerene surface regiospecifically. In contrast, Sc3N@C78- D3 h(5) and Sc3N@C80- Ih show no reactivity toward [(μ-H)3Re3(CO)11(NCMe)], probably due to electronic and steric factors. These complexes can be easily purified by using HPLC. Carbonylation of each complex releases the corresponding higher fullerene or endohedral metallofullerene in pure form. Remarkably, the C86- C2(17) and C86- Cs(16) isomers were successively separated through Re3 cluster complexation/decomplexation. This unique bonding feature may provide an attractive general strategy to purify as yet unresolved fullerene mixtures. [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]

Reaction of C60and W(CO)(PhCCPh)3in refluxing o-dichlorobenzene affords thefullerene complexes W(CO)(η2-C2Ph2)(η2-C60)(η4-C4Ph4) (4) and W(CPh)(CO)(η2-C60)(η5-C5Ph5) (5) and the η3-benzyl complex W(CO)2(η5:η3-C5Ph4(o-C6H4)CHPh) (6). The carbocylic groups in these compounds are arising from[2 2] and [2 2 1] cycloaddition of the diphenylacetylene ligands,likely induced by coordination of the bulky C60molecule.The structures of 4and 6have been determinedby an X-ray diffraction study. [ABSTRACT FROM AUTHOR]