Formation of single-bonded (C60-)2 and (C70-)2 dimers in crystalline ionic complexes of fullerenes

New ionic complexes of fullerenes C(60) and C(70) with decamethylchromocene Cp*(2)Cr.C60.(C(6)H(4)Cl(2))(2) (1), Cp*(2)Cr.C60.(C(6)H(6))(2) (2); the multicomponent complex of (Cs(+))(C70-) with cyclotriveratrylene CTV.(Cs)(2).(C70)(2).(DMF)(7).(C(6)H(6))(0.75) (3); bis(benzene)chromium Cr(C(6)H(6))(2).C60.(C(6)H(4)Cl(2))(0.7) (4), Cr(C(6)H(6))(2).C60.C(6)H(5)CN (5), Cr(C(6)H(6))(2).C70.C(6)H(4)Cl(2) (6), Cr(C(6)H(6))(2).C60 (7); cobaltocene Cp(2)Co.C60.C(6)H(4)Cl(2) (8), Cp(2)Co.C70.(C(6)H(4)Cl(2))(0.5) (9); and cesium Cs.C70.(DMF)(5) (10) have been obtained. The complexes have been characterized by the elemental analysis, IR-, UV-vis-NIR spectroscopy, EPR and SQUID measurements. It is shown that C(60)(.-) exists as a single-bonded diamagnetic (C60-)2 dimer in 1, 2, 4, 5, and 8 at low temperatures (1.9-250 K). The dimers dissociate above 160-250 K depending on donor and solvent molecules involved in the complex. C60(.-) dimerizes reversibly and shows a small hysteresis (<2 K) at slow cooling and heating rates. The single-bonded diamagnetic (C70-)2 dimers are also formed in 6, 9, and 10 and begin to dissociate only above 250-360 K. The IR and UV-vis-NIR spectra of sigma-bonded negatively charged fullerenes are presented.     

The Interaction of C60, C70, and C60(CN)2 radical anions with cobalt(II) tetraphenylporphyrin in solid multicomponent complexes

A method for the synthesis of the multicomponent ionic complexes: [Cr(I)(C(6)H(6))(2) (.+)][Co(II)(tpp)(fullerene)(-)].C(6)H(4)Cl(2), comprising bis(benzene)chromium (Cr(C(6)H(6))(2)), cobalt(II) tetraphenylporphyrin (Co(II)(tpp)), fullerenes (C(60), C(60)(CN)(2), and C(70)), and o-dichlorobenzene (C(6)H(4)Cl(2)) has been developed. The monoanionic state of the fullerenes has been proved by optical absorption spectra in the UV/vis/NIR and IR ranges. The crystal structures of the ionic [[Cr(I)(C(6)H(6))(2)](.+)](1.7)[[Co(II)(tpp)(C(60))](2)](1.7-). 3.3 C(6)H(4)Cl(2) and [[Cr(I)(C(6)H(6))(2)] (.+)](2)[Co(II)(tpp)[C(60)(CN)(2)]](-)[C(60)(CN)(2) (.-)]).3 C(6)H(4)Cl(2) are presented. The essentially shortened Co.C(fullerene) bond lengths of 2.28-2.32 A in these complexes indicate the formation of sigma-bonded [Co(II)(tpp)][fullerene](-) anions, which are diamagnetic. All the ionic complexes are semiconductors with room temperature conductivity of 2 x 10(-3)-4 x 10(-6) S cm(-1), and their magnetic susceptibilities show Curie-Weiss behavior. The neutral complexes of Co(II)(tpp) with C(60), C(60)(CN)(2), C(70), and Cr(0)(C(6)H(6))(2), as well as the crystal structures of [Co(II)(tpp)](C(60)).2.5 C(6)H(4)Cl(2), [Co(II)(tpp)](C(70)). 1.3 CHCl(3).0.2 C(6)H(6), and [Cr(0)(C(6)H(6))(2)][Co(II)(tpp)] are discussed. In contrast to the ionic complexes, the neutral ones have essentially longer Co.C(fullerene) bond lengths of 2.69-2.75 A.     

Synthesis of two pentaarylated [60]fullerene derivatives Ar_5C_(60)-H (Ar = p-MeC_6H_4, m-MeC_6H_4) and their novel electrochemical properties

Through one pot reaction of C60 with organocopper/magne-sium reagent ( p - MeQ H4 )2 CuMgBr or ( m - MeC6 H )2 -CuMgBr prepared from CuBr-Me2S and p-MeC6H4MgBr or m-MeC6H4MgBr and subsequent quenching with aqueous NH4Cl, two pentaarylated [60] fullerene derivatives (p-MeC6H4)5C60H (1) and (m-MeC6H4)5C60H (2) have been synthesized in 94% and 96% yields, respectively. While known compound 1 prepared via this improved method is unambiguously identified, new compound 2 is fully characterized by elemental analysis, IR, UV-vis, 1H NMR and 13C NMR spectroscopies. Additionally, electrochemical study shows that the two [60] fullerene derivatives 1 and 2 in dichloromethane solution display two sequential one-electron reductions which are shifted by about 0.4V towards more negative potential values with respect to free C60. Such remarkable cathodic shift is attributed to the multiple breakage of the double-bond conjugation within the fullerene core.     

Synthesis of the phosphino-fullerene PPh2(o-C6H4)(CH2NMeCH)C60 and its function as an η1-P or η3-P,C2 ligand

Following the method of Prato et al., reaction of C(60), N-methylglycine and o-(diphenylphosphino)benzaldehyde affords PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60) (1) in moderate yield. Compound 1 reacts with W(CO)(4)(NCMe)(2) to produce W(CO)(4)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (2), through coordination of the phosphine group and one 6 : 6-ring junction of fullerene. Reaction of 1 and Os(3)(CO)(11)(NCMe) affords Os(3)(CO)(11)(PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (3), which undergoes a cluster fragmentation reaction in refluxing toluene to produce Os(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (4). Thermal reaction of 1 and Os(3)(CO)(12) affords 3 and 4. On the other hand, reaction of 1 and Ru(3)(CO)(12) yields only the mononuclear complex Ru(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (5). The structures of 1-3 and 5 were determined by an X-ray diffraction study.     

Synthetic, electrochemical, and theoretical studies of tetrairidium clusters bearing mono- and bis[60]fullerene ligands

Heating a mixture of Ir(4)(CO)(9)(PPh(3))(3) (1) and 2 equiv of C(60) in refluxing chlorobenzene (CB) affords a "butterfly" tetrairidium-C(60) complex Ir(4)(CO)(6){mu(3)-kappa(3)-PPh(2)(o-C(6)H(4))P(o-C(6)H(4))PPh(eta(1)-o-C(6)H(4))}(mu(3)-eta(2):eta(2):eta(2)-C(60)) (3, 36%). Brief thermolysis of 1 in refluxing chlorobenzene (CB) gives a "butterfly" complex Ir(4)(CO)(8){mu-k(2)-PPh(2)(o-C(6)H(4))PPh}{mu(3)-PPh(2)(eta(1):eta(2)-o-C(6)H(4))} (2, 64%) that is both ortho-phosphorylated and ortho-metalated. Interestingly, reaction of 2 with 2 equiv of C(60) in refluxing CB produces 3 (41%) by C(60)-assisted ortho-phosphorylation, indicating that 2 is the reaction intermediate for the final product 3. On the other hand, reaction of Ir(4)(CO)(8)(PMe(3))(4) (4) with excess (4 equiv) C(60) in refluxing 1,2-dichlorobenzene, followed by treatment with CNCH(2)Ph at 70 degrees C, affords a square-planar complex with two C(60) ligands and a face-capping methylidyne ligand, Ir(4)(CO)(3)(mu(4)-CH)(PMe(3))(2)(mu-PMe(2))(CNCH(2)Ph)(mu-eta(2):eta(2)-C(60))(mu(4)-eta(1):eta(1):eta(2):eta(2)-C(60)) (5, 13%) as the major product. Compounds 2, 3, and 5 have been characterized by spectroscopic and microanalytical methods, as well as by single-crystal X-ray diffraction studies. Cyclic voltammetry has been used to examine the electrochemical properties of 2, 3, 5, and a related known "butterfly" complex Ir(4)(CO)(6)(mu-CO){mu(3)-k(2)-PPh(2)(o-C(6)H(4))P(eta(1)-o-C(6)H(4))}(mu(3)-eta(2):eta(2):eta(2)-C(60)) (6). These cyclic voltammetry data suggest that a C(60)-mediated electron transfer to the iridium cluster center takes place for the species 3(3)(-) and 6(2)(-) in compounds 3 and 6. The cyclic voltammogram of 5 exhibits six well-separated reversible, one-electron redox waves due to the strong electronic communication between two C(60) cages through a tetrairidium metal cluster spacer. The electrochemical properties of 3, 5, and 6 have been rationalized by molecular orbital calculations using density functional theory and by charge distribution studies employing the Mulliken and Hirshfeld population analyses.     

C3v-symmetrical tribenzotriquinacenes as hosts for C60 and C70 in solution and in the solid state

Various tribenzotriquinacenes (TBTQs), most of which incorporate six functional groups at the periphery of their C3v-symmetrical, rigid and convex-concave molecular framework, have been studied with respect to their ability to form supramolecular complexes with the C60 and C70 fullerenes, either in the solid state or in solution. The hexabromo derivative Br6-TBTQ was cocrystallized with C60 as [Br6-TBTQ相似文献   

Selective preparation of oxygen-rich [60]fullerene derivatives by stepwise addition of tert-butylperoxy radical and further functionalization of the fullerene mixed peroxides

tert-Butylperoxy radicals add to C(60) selectively to form multi-adducts C(60)(O)(m)(OO(t)Bu)(n) (m = 0, n = 2, 4, 6; m = 1, n = 0, 2, 4, 6) in moderate yields under various conditions. Visible light irradiation favors epoxide formation. High concentration of tert-butylperoxy radicals mainly produces the hexa-homoadduct C(60)(OO(t)Bu)(6) 6; low concentration and long reaction time favor the epoxy-containing C(60)(O)(OO(t)Bu)(4) 7. The reaction can be stopped at the bis-adducts with limited TBHP. A stepwise addition mechanism is discussed involving mono-, allyl-, and cyclopentadienyl C(60) radical intermediates. m-CPBA reacts with the 1,4-bis-adduct to form C(60)(O)(OO(t)Bu)(2) and C(60)(O)(3)(OO(t)Bu)(2). The C-O bond of the epoxy ring in 7 can be cleaved with HNO(3) and CF(3)COOH. Nucleophilic addition of NaOMe to 7 follows the S(N)1 and extended S(N)2' mechanism, from which four products are isolated with the general formula C(60)(O)(a)(OH)(b)(OMe)(c)(OO(t)Bu)(d). Visible light irradiation of the hexa-adduct 6 results in partial cleavage of both the C-O and O-O bonds of peroxide moieties and formation of the cage-opened compound C(60)(O)(O)(2)(OO(t)Bu)(4). All the fullerene derivatives are characterized by spectroscopic data. A single-crystal structure has been obtained for an isomer of C(60)(O)(OH)(2)(OMe)(4)(OO(t)Bu)(2).     

Bromination-mediated regioselective preparation of cyclopentadienyl-type [60]fullerene derivatives with alkoxy, peroxy, and bromo or hydro addends

Bromine reacts with the 1,2-bisadduct C(60)(OOtBu)(2) efficiently to form the cyclopentadienyl-type compound 4 (C(60)(OOtBu)(2)Br(4)). In the presence of AgClO(4), the four bromine atoms can be replaced regioselectively by methoxyl groups in a stepwise fashion to form C(60)(OOtBu)(2)Br(4-x)(OMe)(x). A second alcohol may be introduced by treating partially methoxylated compound 6 (C(60)(OOtBu)(2)Br(2)(OMe)(2)) with ROH/AgClO(4). Other related reactions have been investigated to explore the reactivity patterns. The structure of compound 6 was confirmed by single crystal X-ray analysis.     

Peculiarities of C60*- coordination to cobalt(II) octaethylporphyrin in ionic multicomponent complexes: Observation of the reversible formation of Co-C(C60-) coordination bonds

Ionic multicomponent complexes containing the C60- anion, cobalt(II) octaethylporphyrin (OEP), and the noncoordinating tetramethylphosphonium cation (TMP+), [(TMP+){Co(II)OEP(C60-)}(C6H5CN)x(C6H4Cl2)(1-x)] (x congruent with 0.75) (1), or the coordinating cation of N-methyldiazabicyclooctane (MDABCO+), [{(MDABCO+)Co(II)OEP(C60-)}(C6H5CN)x(C6H4Cl2)(1-x)] (x congruent with 0.67) (2), were obtained. Diamagnetic sigma-bonded {Co(II)OEP(C60-)} units in 1 have the Co...C(C60-) distance of 2.268(1) A at 100 K and are stable up to 290 K. Both MDABCO+ and C60- coordinate to Co(II)OEP in 2. In this case, a noticeably longer Co...CC60-) distance of 2.508(4) A was observed at 100 K. As a result, the unprecedented reversible formation of the Co-C(C60-) coordination sigma bond is realized in 2 and is accompanied by a transition from a paramagnetic to a diamagnetic state in the 50-250 K range. It was shown, for the first time, that the Co...C distance of about 2.51 A is a boundary distance below which the Co-C(C60-) coordination bond is formed.     

HC60CH2C6H5的结构及光谱的理论研究

用ＩＮＤＯ系列方法研究了由Ｃ６０＾２－制备的衍生物ＨＣ６０ＣＨ２Ｃ６Ｈ５的结构和ＵＶ光谱。结果表明，六元环上的１，２－异构体具有Ｃｓ对称性，１，４－异构体具有Ｃ１对称性。以优化构型为基础，计算两种加成产物的ＵＶ光谱，表明１，２－异构体的特征吸收与实验值相符；同时，对１，４－异构体的ＵＶ光谱进行了理论预测，对电子跃迁进行了理论指认，并分析了光谱红移的原因。     

Synthesis and crystal structure of ionic multicomponent complex: ([Cr(I)(PhH)(2)].+))(2)[Co(II)TPP(C(60)(CN)(2))]-[C(60)(CN)(2)](.-).3(o-C(6)H(4)Cl(2)) containing C(60)(CN)(2).- radical anion and sigma-bonded diamagnetic Co(II)TPP(C(60)(CN)(2)) -anion

The ionic multicomponent complex complex: ([Cr(I)(PhH)(2)].+))(2)[Co(II)TPP(C(60)(CN)(2))]-[C(60)(CN)(2)](.-).3(o-C(6)H(4)Cl(2)) (Co(II)TPP: cobalt (II) tetraphenylporphyrin; Cr(PhH)(2): bis(benzene)chromium; o-C(6)H(4)Cl(2): o-dichlorobenzene) containing CoTPP(C(60)(CN)(2)- anion and C(60)(CN)(2).- radical anion was obtained. The complex has the cage structure with channels, which accommodate Cr(I)(PhH)(2)(.+) and o-C(6)H(4)Cl(2) molecules. For the first time the sigma-bonding of Co(II)TPP to the fullerene radical anion with the essentially shortened Co.C(C(60)(CN)(2)) contact of 2.282 A is observed. The sigma-bonding results in the diamagnetism of Co(II)TPP(C(60)(CN)(2))(-) anion. The nonbonded C(60)(CN)(2)(.-) radical anion retains both the C(2)(v)symmetry and the shape of the molecule. The length of the C(triple bond)N bonds is 1.141 and 1.152 A.     

Formation of antiferromagnetically coupled C(60)(*)(-) and diamagnetic (C(70)(-))(2) dimers in ionic complexes of fullerenes with (MDABCO(+))(2).M(II)TPP (M = Zn, Co, Mn, and Fe) assemblies

A series of ionic multicomponent complexes comprising C60 and C70 anions and coordinating assemblies of methyldiazabicyclooctane cations with metal tetraphenylporphyrins, (MDABCO+)2.MIITPP.(C60(70)-)2.Sol. (C60, M = Zn (1); C60, M = Co (2); C60, M = Mn (3); C60, M = Fe (4); C70, M = Mn (5); and C70, M = Fe (6)) has been obtained. IR- and UV-vis-NIR spectra of 1-6 justified the formation of C60*- in 1-4 and single-bonded (C70-)2 dimers in 5 and 6. Co and Mn atoms are six-coordinated in the (MDABCO+)2.MIITPP units with relatively long M-N bonds of 2.475(2), 2.553(2), and 2.511(3) A for 2, 3, and 5, respectively. Isostructural complexes 2 and 3 contain C60*- zigzag chains separated by the (MDABCO+)2.MIITPP units, whereas in 5 the layers formed by the (C70-)2 dimers alternate with those composed of the (MDABCO+)2.MnIITPP units and noncoordinating MDABCO+ cations. Negative Weiss constants of -13 (1), -2 (3), and -2 (4) K indicate the antiferromagnetic interaction of spins, which decreases the magnetic moment of the complexes below 70-120 K. The EPR signals of 1 and 4 attributed to C60*- are split into two components at the same temperatures, which broaden and shift to higher and lower magnetic fields with the temperature decrease. Complexes 2 and 3 show single EPR signals with g-factors equal to 2.1082 and approximately 2.4 at 293 K, respectively. These values are mean between those characteristic of MIITPP and C60*-, and, consequently, the signals appear due to exchange coupling between these paramagnetic species. The antiferromagnetic ordering of C60*- spins below 70-100 K shifts g-factor values closer to those characteristic of individual MIITPP (g = 2.1907 (2) and approximately 4.9 (3) at 4 K). In contrast to 1-4, complex 5 shows paramagnetic behavior with Weiss constant close to 0.     

Crystal structure and magnetic properties of an ionic C60 complex with decamethylcobaltocene: (Cp*2Co)2C60(C6H4Cl2, C6H5CN)2. Singlet-triplet transitions in the C60(2-) anion

The C(60) complex with decamethylcobaltocene, (Cp(2)Co)(2)C(60)(C(6)H(4)Cl(2), C(6)H(5)CN)(2) (1) (C(6)H(4)Cl(2) = 1,2-dichlorobenzene; C(6)H(5)CN = benzonitrile), has been obtained as single crystals by the diffusion method. The IR and UV-vis-NIR spectra show the presence of the C(60)(2)(-) and the Cp(2)Co(+) ions, which form a three-dimensional framework with channels accommodating solvent molecules. EPR and SQUID measurements show that C(60)(2)(-) has a diamagnetic singlet (S = 0) state in the 2-140 K range. The appearance of a broad EPR signal and the increase in magnetic susceptibility of 1 above 140 K are assigned to a thermal population of a close lying triplet (S = 1) state. The singlet-triplet energy gap for C(60)(2)(-) in solid 1 is estimated to be 730+/-10 cm(-)(1).     

Complexes of gold(I), silver(I), and copper(I) with pentaaryl[60]fullerides

Gold(I), silver(I), and copper(I) phosphine complexes of 6,9,12,15,18-pentaaryl[60]fullerides 1a and 1b, namely, [(4-MeC(6)H(4))(5)C(60)]Au(PPh(3)) (2a), [(4-t-BuC(6)H(4))(5)C(60)]Au(PPh(3)) (2b), [(4-MeC(6)H(4))(5)C(60)]Ag(PCy(3)) (3a), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PPh(3)) (3b), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PCy(3)) (3c), [(4-MeC(6)H(4))(5)C(60)]Cu(PPh(3)) (4a), and [(4-t-BuC(6)H(4))(5)C(60)]Cu(PPh(3)) (4b), have been synthesized and characterized spectroscopically. All complexes except for 3c were also characterized by single-crystal X-ray diffraction. Several coordination modes between the cyclopentadienyl ring embedded in the fullerene and the metal centers are observed, ranging from η(1) with a slight distortion toward η(3) in the case of gold(I), to η(2)/η(3) for silver(I), and η(5) for copper(I). Silver complexes 3a and 3b are rare examples of crystallographically characterized Ag(I) cyclopentadienyls whose preparation was possible thanks to the steric shielding provided by fullerides 1a and 1b, which stabilizes these complexes. Silver complexes 3a and 3b both display unexpected coordination of the cyclopentadienyl portion of the fulleride anion with Ag(I). DFT calculations on the model systems (H(5)C(60))M(PH(3)) and CpMPH(3) (M = Au, Ag, or Cu) were carried out to probe the geometries and electronic structures of these metal complexes.     

Two metal centers bridging two C60 cages as a wide passage for efficient interfullerene electronic interaction

The reaction of Ir4(CO)8(PMe3)4 with excess C60 in refluxing 1,2-dichlorobenzene, followed by treatment by CNR (R = CH2C6H5) at 70 degrees C, affords a fullerene-metal sandwich complex Ir4(CO)3(mu4-CH)(PMe3)2(mu-PMe2)(CNR)(mu-eta2,eta2-C60)(mu4-eta1,eta1,eta2,eta2-C60) (1), which exhibits an interesting structural feature of two metal atoms bridging the two C60 centers as well as the first example of a mu4-eta1,eta1,eta2,eta2-C60 bonding mode. Compound 1 has been characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction study. A cyclic voltammetry study reveals strong electronic communication between the two C60 centers in 1, which is due to the presence of a wide channel of two metal centers between the two C60 cages for efficient electronic interaction.     

含烯烃配体的过渡金属卡宾配合物的研究 XIII: π-环戊二烯基(二羰基)(芳酰基)铁配合物的新合成法及其晶体结构

用环戊二烯(三羰基铁)与芳基锂在低温时反应, 生成的酰羰基锂盐随后在CH2Cl2中于-60℃或在水溶液中于0℃用Et3OBF4烷基化, 以中等产率获得组成为C5H5(CO)2Fe(COAr)的5个π-环戊二烯基(二羰基)(芳甲酰基)铁络合物, 新化合物用元素分析, IR, HNMR和质谱鉴定了, 并用X射线衍射研究了C5H5(CO)2Fe(p-CF3C6H4CO)的晶体结构.     

Iron Sulfido Derivatives of the Fullerenes C(60) and C(70)

Toluene solutions of C(60) react upon UV irradiation with Fe(2)S(2)(CO)(6) to give C(60)[S(2)Fe(2)(CO)(6)](n)() where n = 1-6. C(60)[S(2)Fe(2)(CO)(6)](n)() where n = 1-3 have been isolated and characterized. Crystallographic studies of C(60)S(2)Fe(2)(CO)(6) show that the S-S bond of the Fe(2) reagent is cleaved to give a dithiolate with idealized C(2)(v)() symmetry. The addition occurred at a 6,6 fusion, and the metrical details show that the Fe(2) portion of the molecule resembles C(2)H(4)S(2)Fe(2)(CO)(6). IR spectroscopic measurements indicate that the Fe(2)(CO)(6) subunits in the multiple-addition species (n > 1) interact only weakly. UV-vis spectra of the adducts show a shift to shorter wavelength with addition of each S(2)Fe(2)(CO)(6) unit. Photoaddition of the phosphine complex Fe(2)S(2)(CO)(5)(PPh(3)) to C(60) gave C(60)[S(2)Fe(2)(CO)(5)(PPh(3))](n)(), where n = 1-3. (31)P{(1)H} NMR studies show that the double adduct consists of multiple isomers. Photoaddition of Fe(2)S(2)(CO)(6) to C(70) gave a series of adducts C(70)[S(2)Fe(2)(CO)(6)](n)() where n = 1-4. HPLC analyses show one, four, and three isomers for the adducts, respectively.     

He+C60↔(He@C60)的反应势垒研究

The reaction barriers of (He+C60(He＠60)) have been calculated by the quantum-chemical method EHMO/ASED in the following four paths: (1) penetrate through the pentagon on the C60 cage; (2) penetrate through the hexagon on the C60 cage,(3) penetrate through the short bond; (4) penetrate through the long bond. Corresponding to each path, there are two choices: (a) while He penetrate C60 cage, the distances of the C’s which are the most adjacent to He are changed with a planar extension and a concerned window is formed; (b) while He penetrate C60 cage, the distances of the C’s which are the most adjacent to He are changed with a spherical extension and a concerned window is formed. The results are given in Figs. 1-2 and Tables 1-2. It is shown that the reaction through path(4) with choice (a) has the least reaction barrier, being optimum. At that case, a window of 9-membered ring is formed. Because the window extension of C6H6 is more free than that of C60, the barrier of He penetrating through C6H6 will be lower than that of He penetrating through C60.     

C60-induced alkyne-alkyne coupling and alkyne scission reactions of a tungsten tris(diphenylacetylene) complex

Reaction of W(NCMe)(η(2)-PhC≡CPh)(3) with C(60) affords W(η(3)-NC(Me)C(60))(η(4),η(2)-C(6)Ph(6)) (2) and W(≡CPh)(NCMe)(η(2)-C(60)) (η(3),η(2)-C(5)Ph(5)) (3). The hexaphenylbenzene species of 2 shows an η(4)-butadiene + η(2)-olefin bonding mode and the nitrile carbon is inserted into one 6:5-ring junction of C(60). Compound 3 contains an η(3),η(2)-pentaphenylcyclopentadienyl and a benzylidyne group from 2 + 2 + 1 cyclization and scission reactions of the diphenylacetylene ligands.     

Mechanochemical Reactions of Fullerenes under High-Speed Vibration Milling

Since a novel technique called "high-speed vibration milling" (HSVM) was first applied to the Reformatskytype reaction of C60 in 1996, [1] this technique has been applied to various kinds of fullerene functionalizations including the preparation of C120. [2] Most recent reactions of fullerenes under HSVM conditions will be discussed: (1)reaction of C60/C70 with N-alkylglycines and aldehydes (Scheme 1); (2) reaction of C60 with active methylene compounds in the presence of bases (Scheme 2); (3) reaction of C6o with diazo compounds (Scheme 3); (4) reaction of C6o with anthracene derivatives (Scheme 4).