Theoretical investigation of C56 fullerene isomers and related compounds

All the 924 classical isomers of fullerene C(56) have been investigated by PM3, and some most stable isomers are refined with HCTH/3-21G and B3LYP6-31G(d) methods. D(2):003 with the least number of adjacent pentagons is predicted to be the most stable isomer at B3LYP/6-31G(d) level, while C(s):022 and C(2):049 possess nearly degenerate energies with relative energies of 0.03 and 3.90 kcal/mol, respectively. However, as to dianionic C(56)(2-) fullerene, C(2v):011 is predicted to be the most stable isomer. Investigations also show that the encapsulation of Ca atom in C(56) fullerene is exothermic and the metallofullerenes Ca@C(56) can be described as Ca(2+)@C(56)(2-). The computed relative stabilities show that the D(2):003 behaves more thermodynamically stable than other isomers in a wide temperature interval, and C(2v):011 should also be an important component. The electronic isomerization of C(56) (C(2v):011) and C(50) (D(5h):002) indicates that this phenomenon might be rather general in fullerenes and causes different properties, thus bringing about new possible applications of fullerenes. The static second-order hyperpolarizabilities of the three most stable isomers are slightly larger than that of C(60).     

Search for more stable C58X18 isomers: stabilities and electronic properties of seven-membered ring C58X18 fullerene derivatives (X = H, F, and Cl)

Stimulated by recent preparation and characterization of the first C58F18 fullerene derivative, with a heptagon in the framework (Science, 2005, 309, 278), we have performed systematic density functional studies on the stabilities and electronic properties of two different structures C58X18 (A) and C58X18 (B), where X = H, F, and Cl. The large energy gaps between the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals (between 2.64 and 3.45 eV) and the aromatic character (with nucleus independent chemical shifts from -10.0 to -13.9 ppm) of C58X18 (A) and C58X18 (B) indicate that they possess high stabilities. Further investigations show that the heats of formation of C58X18 fullerene derivatives are highly exothermic, suggesting that adding nine X2's releases much of the strain of pure C58 fullerene and leads to stabilities of the derivatives. Lower in energy and stronger in aromatic character than C58F18 (B), which has been experimentally characterized, C58F18 (A) should also be isolated. In addition, C58F18 and C58Cl18 are predicted to possess large electron affinities, especially for C58F18 (B) and C58Cl18 (B) with values of 3.00 and 3.06 eV, respectively, even larger than that (2.50 eV) of C60F18. Hence, C58F18 and C58Cl18 can serve as good electron-acceptors with possible photonic/photovoltaic application. The IR spectra of C58X18 are simulated to facilitate identification of different isomers experimentally. In addition, the electronic spectra and second-order hyperpolarizabilities of C58X18 are predicted by ZINDO and sum-over-states model. With the addition of 9X2, both the static and frequency-dependent second-order hyperopolarizabilities of C58X18 greatly decrease compared to those of C58.     

Arbuzov chemistry with chlorofullerene C(60)Cl(6): a powerful method for selective synthesis of highly functionalized [60]fullerene derivatives

We report Arbuzov-type reactions of chlorofullerene C(60)Cl(6) with trialkyl phosphites producing highly functionalized fullerene derivatives C(60)[P(O)(OR)(2)](5)H with high yields. The designed family of [60]fullerene phosphonic acids and their esters showed unusual properties which might find valuable material science applications.     

Electron attachment to C(2)Cl(4) and Trojan horse ionization

In a recent study of tetrachloroethylene, the anion yield curves were analyzed using three published negative-ion Morse potentials. Unexpected ions at zero electron energy were explained by the "Trojan horse" mechanism. This communication also attributes formation of Cl(2)(-) at higher energies to a Trojan horse mechanism. Six new Morse potentials are calculated to account for the observed anion states. These combine all extant electron impact and attachment data. The electron affinity of the C(2)Cl(3) radical, 3.1(1) eV, and the C-Cl bond dissociation energy 4.0(1) eV are reported.     

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.     

Optical excitation and absorption spectra of C50Cl10

C50Cl10 [S. Y. Xie et al., Science 304, 699 (2004)] has been synthesized in large quantities enabling the capture of the labile fullerene C50. In this Communication, we report ab initio calculations on the optical excitation and absorption spectra of C50Cl10. We successfully explain and assign the measured UV-visible absorption spectrum of C50Cl10. The first singlet excitation for C50Cl10 is optically forbidden, and its optical absorption gap is redshifted by 0.6 eV (110 nm) relative to that of C60. We demonstrate that passivating C50 with 10 hydrogen atoms and replacing one Cl in C50Cl10 by one methoxy group lead to 100 nm blueshift and 90 nm redshift of the optical gap predicted for C50Cl10, respectively, suggesting C50 derivatives are suitable for tunable optical applications.     

C_(56)X_(10)(X=F,Cl,Br,I)的结构稳定性和电子性质

采用密度泛函理论(DFT)中的广义梯度近似(GGA)方法对C56X10(X=F,Cl,Br,I)的结构稳定性和电子性质进行了计算研究.结构稳定性计算表明:对于C56X10(X=F,Cl,Br,I),能隙、反应热、最大振动频率和最小振动频率都随着X原子序数的增加而减小,表明C56X10(X=F,Cl,Br,I)的稳定性随着X原子序数的增加而逐渐降低,其中C56F10最为稳定.前人在实验上已成功合成出C56Cl10,因此,我们推测C56F10有望在实验上成功合成.前线轨道计算发现,C56相邻的五边形公共顶点以及两个六边形-五边形-六边形公共顶点是笼子中化学活性最强的部位,有利于卤族元素的外部吸附.此外,计算结果还显示,C56X10(X=F,Cl,Br,I)的电负性随着X原子序数的增大而逐渐减弱,C—X基团的电负性因位置的不同而不同.     

Synthesis and antiviral activity of highly water-soluble polycarboxylic derivatives of [70]fullerene

We report here a facile preparation of highly water-soluble derivatives C(70)[p-C(6)H(4)(CH(2))(n)COOH](8) (n = 2, 3) starting from readily available chlorinated [70]fullerene precursors C(70)Cl(8) and C(70)Cl(10). The synthesized fullerene derivatives showed pronounced antiviral activity in vitro, particularly against human immunodeficiency virus (HIV) and influenza A virus (subtypes H1N1 and H3N2).     

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.     

MX3(-) superhalogens (M = Be, Mg, Ca; X = Cl, Br): a photoelectron spectroscopic and ab initio theoretical study

Gas-phase alkaline earth halide anions, MgX3(-) and CaX3(-) (X = Cl, Br), were produced using electrospray and investigated using photoelectron spectroscopy at 157 nm. Extremely high electron binding energies were observed for all species and their first vertical detachment energies were measured as 6.60 +/- 0.04 eV for MgCl3(-), 6.00 +/- 0.04 eV for MgBr3(-), 6.62 +/- 0.04 eV for CaCl3(-), and 6.10 +/- 0.04 eV for CaBr3(-). The high electron binding energies indicate these are very stable anions and they belong to a class of anions, called superhalogens. Theoretical calculations at several levels of theory were carried out on these species, as well as the analogous BeX3(-). Vertical detachment energy spectra were predicted to compare with the experimental observations, and good agreement was obtained for all species. The first adiabatic detachment energies were found to be substantially lower (by about 1 eV) than the corresponding vertical detachment energies for all the MX3(-) species, indicating extremely large geometry changes between MX3(-) and MX3. We found that all the MX3(-) anions possess D3h ((1)A1') structures and are extremely stable against dissociation into MX2 and X-. The corresponding neutral species MX3, however, were found to be only weakly bound with respect to dissociation toward MX2 + X. The global minimum structures of all the MX3 neutrals were found to be C2v ((2)B2), which can be described as (X2(-))(MX+) charge-transfer complexes, whereas the MX2...X (C2v, (2)B1) van der Waals complexes were shown to be low-lying isomers.     

C20 carbon clusters: fullerene-boat-sheet generation, mass selection, photoelectron characterization

Electron-impact ionization in a time-of-flight mass spectrometer of C(20)H(0-3)Br(14-12) probes-secured from C(20)H(20) dodecahedrane by a "brute-force" bromination protocol-provided bromine-free C(20)H(0-2(3)) anions in amounts that allowed the clean mass-separation of the hydrogen-free C(20) (-) ions and the photoelectron (PE) spectroscopic characterization as C(20) fullerene (electron affinity (EA)=2.25+/-0.03 eV, vibrational progressions of 730+/-70). The extremely strained C(20) fullerene ions surfaced as kinetically rather stable entities (lifetime of at least the total flight time of 0.4 ms); they only very sluggishly expel a C(2) unit. The HOMO and LUMO are suggested to be almost degenerate (DeltaE=0.27 eV). The assignment as a fullerene was corroborated by the PE characterization of the C(20) bowl (EA=2.17+/-0.03 eV, vibrational progression of 2060+/-50 cm(-1)) analogously generated from C(20)H(10) corannulene (C(20)H(1-3)Br(9-8) samples) and comparably stable. Highly resolved low-temperature PE spectra of the known C(20) ring (EA=2.49+/-0.03 eV, vibrational progressions 2022+/-45 and 455+/-30 cm(-1)), obtained from graphite, display an admixture of, most probably, a bicyclic isomer (EA=3.40+/-0.03 eV, vibrational progression 455+/-30 cm(-1)). The C(20) (+(-)) and C(20)H(2) (+(-)) cluster ions generated from polybrominated perylene (C(20)H(0-2)Br(12-10)) have (most probably) retained the planar perylene-type skeleton (sheet, EA=2.47+/-0.03 eV, vibrational progressions of 2089+/-30 and 492+/-30 cm(-1) and EA=2.18+/-0.03 eV, vibrational progressions of 2105+/-30 and 468+/-30 cm(-1)).     

The extended view on the empty C2(3)-C82 fullerene: isolation, spectroscopic, electrochemical, and spectroelectrochemical characterization and DFT calculations

An extended study of the spectroscopic and redox properties of the C(82) fullerene is presented. Among the nine isolated-pentagon-rule (IPR) isomers of the C(82) fullerene the C(82)(3) isomer with C(2) symmetry is the only stable, empty fullerene structure formed in the arc burning process that can be isolated in an isomerically pure form. Here, its formation and isolation are described and its structure is confirmed by experimental spectroscopic studies as well as time-dependent DFT calculations. The electrochemistry of the C(82)(3) isomer is studied in detail by cyclic voltammetry and spectroelectrochemistry. The anionic species of C(82) with the charge ranging from C(82) (-) to C(82) (4-) were successively generated in o-dichlorobenzene solution at room temperature and characterized by in situ ESR and visible/near-infrared (Vis/NIR) spectroscopy. The data give new insights into the charged states of the C(82)(3) fullerene.     

Photoelectron spectroscopy and the electronic structure of the uranyl tetrachloride dianion: UO(2)Cl(4) (2-)

The uranyl tetrachloride dianion (UO(2)Cl(4) (2-)) is observed in the gas phase using electrospray ionization and investigated by photoelectron spectroscopy and relativistic quantum chemical calculations. Photoelectron spectra of UO(2)Cl(4) (2-) are obtained at various photon energies and congested spectral features are observed. The free UO(2)Cl(4) (2-) dianion is found to be highly stable with an adiabatic electron binding energy of 2.40 eV. Ab initio calculations are carried out and used to interpret the photoelectron spectra and elucidate the electronic structure of UO(2)Cl(4) (2-). The calculations show that the frontier molecular orbitals in UO(2)Cl(4) (2-) are dominated by the ligand Cl 3p orbitals, while the U-O bonding orbitals are much more stable. The electronic structure of UO(2)Cl(4) (2-) is compared with that of the recently reported UO(2)F(4) (2-) [P. D. Dau, J. Su, H. T. Liu, J. B. Liu, D. L. Huang, J. Li, and L. S. Wang, Chem. Sci. 3 1137 (2012)]. The electron binding energy of UO(2)Cl(4) (2-) is found to be 1.3 eV greater than that of UO(2)F(4) (2-). The differences in the electronic stability and electronic structure between UO(2)Cl(4) (2-) and UO(2)F(4) (2-) are discussed.     

New homoleptic organometallic derivatives of vanadium(III) and vanadium(IV): synthesis, characterization, and study of their electrochemical behaviour

The arylation of [VCl3(thf)3] with LiR(Cl), where R(Cl) is a polychlorinated phenyl group [C6Cl5, 2,4,6-trichlorophenyl(tcp), or 2,6-dichlorophenyl (dcp)] gives four-coordinate, homoleptic organovanadium(III) derivatives with the formula [Li(thf)(4)][V(III)(R(Cl))(4)] (R(Cl) = C(6)Cl(5) (1), tcp (2), dcp (3)). The anion [V(III)(C6Cl5)4]- has an almost tetrahedral geometry, as observed in the solid-state structure of [NBu4][V(C6Cl5)4] (1') (X-ray diffraction). Compounds 1-3 are electrochemically related to the neutral organovanadium(IV) species [V(IV)(R(Cl))4] (R(Cl) = C6Cl5 (4), tcp (5), dcp (6)). The redox potentials of the V(IV)/V(III) semisystems in CH2Cl2 decrease with decreasing chlorination of the phenyl ring (E(1/2) = 0.84 (4/1), 0.42 (5/2), 0.25 V (6/3)). All the [V(IV)(R(Cl))4] derivatives involved in these redox couples could also be prepared and isolated by chemical methods. The arylation of [VCl(3)(thf)(3)] with LiC6F5 also gives a homoleptic organovanadium(III) compound, but with a different stoichiometry: [NBu4]2[V(III)(C6F5)5] (7). In this five-coordinate species, the C6F5 groups define a trigonal bipyramidal environment for the vanadium atom (X-ray diffraction). EPR spectra for the new organovanadium compounds 1-6 are also given and analysed in terms of an elongated tetrahedral structure with C(2v) local symmetry. It is suggested that the R(Cl) groups exert a protective effect towards the vanadium centre.     

Thermally stable perfluoroalkylfullerenes with the skew-pentagonal-pyramid pattern: C60(C2F5)4O, C60(CF3)4O, and C60(CF3)6

Reaction of C(60) with CF(3)I at 550 degrees C, which is known to produce a single isomer of C(60)(CF(3))(2,4,6) and multiple isomers of C(60)(CF(3))(8,10), has now been found to produce an isomer of C(60)(CF(3))(6) with the C(s)-C(60)X(6) skew-pentagonal-pyramid (SPP) addition pattern and an epoxide with the C(s)-C(60)X(4)O variation of the SPP addition pattern, C(s)-C(60)(CF(3))(4)O. The structurally similar epoxide C(s)-C(60)(C(2)F(5))(4)O is one of the products of the reaction of C(60) with C(2)F(5)I at 430 degrees C. The three compounds have been characterized by mass spectrometry, DFT quantum chemical calculations, Raman, visible, and (19)F NMR spectroscopy, and, in the case of the two epoxides, single-crystal X-ray diffraction. The compound C(s)-C(60)(CF(3))(6) is the first [60]fullerene derivative with adjacent R(f) groups that are sufficiently sterically hindered to cause the (DFT-predicted) lengthening of the cage (CF(3))C-C(CF(3)) bond to 1.60 A as well as to give rise to a rare, non-fast-exchange-limit (19)F NMR spectrum at 20 degrees C. The compounds C(s)-C(60)(CF(3))(4)O and C(s)-C(60)(C(2)F(5))(4)O are the first poly(perfluoroalkyl)fullerene derivatives with a non-fluorine-containing exohedral substituent and the first fullerene epoxides known to be stable at elevated temperatures. All three compounds demonstrate that the SPP addition pattern is at least kinetically stable, if not thermodynamically stable, at temperatures exceeding 400 degrees C. The high-temperature synthesis of the two epoxides also indicates that perfluoroalkyl substituents can enhance the thermal stability of fullerene derivatives with other substituents.     

An entrant of smaller fullerene: C56 captured by chlorines and aligned in linear chains

A smaller fullerene C56 (#913) is stabilized, isolated, and crystallographically characterized as C56Cl10. The geometric parameters of C56Cl10 imply the otherwise unstable cage of C56 can be stabilized by chlorination through releasing its surface strains and maintaining fragmental aromaticity. An unexpected C Cl...ClC short contact, as well as the linear alignment with pearl-necklace-shaped, is revealed in C56Cl10 crystal.     

Developing Reagents To Orient Fullerene Derivatives. Formation and Structural Characterization of (eta(2)-C(60)O)Ir(CO)Cl(As(C(6)H(5))(3))(2)

In order to obtain crystals of fullerene oxides that are suitable for single-crystal X-ray diffraction, the reactions between C(60)O and Vaska type iridium complexes have been examined. While reaction with Ir(CO)Cl(P(C(6)H(5))(3))(2)(and with triphenylphosphine but not triphenylarsine) results in partial deoxygenation of the fullerene epoxide, reaction with Ir(CO)Cl(As(C(6)H(5))(3))(2)()()produces crystalline (eta(2)-C(60)O)Ir(CO)Cl(AsPh(3))(2).4.82C(6)H(6).0.18CHCl(3). Black triangular prisms of (eta(2)-C(60)O)Ir(CO)Cl(AsPh(3))(2).4.82C(6)H(6).0.18CHCl(3)form in the monoclinic space group P2(1)/n with a = 14.662(2) ?, b = 19.836(2) ?, c = 28.462(5) ?, and beta = 100.318(12) degrees at 123 (2) K with Z = 4. Refinement (on F(2)) of 10 472 reflections and 1095 parameters with 10 restraints yielded wR2 = 0.152 and a conventional R = 0.066 (for 7218 reflections with I > 2.0sigma(I)). The structure shows that the iridium complex is bound to a 6:6 ring junction of the fullerene with four partially occupied sites for the epoxide oxygen atom. Thus, while deoxygenation of the fullerene does not occur upon reaction with Ir(CO)Cl(AsPh(3))(2), there is a greater degree of disorder in (eta(2)-C(60)O)Ir(CO)Cl(AsPh(3))(2)than previously reported for (eta(2)-C(60)O)Ir(CO)Cl(PPh(3))(2).     

Chlorofullerene C60Cl6: a precursor for straightforward preparation of highly water-soluble polycarboxylic fullerene derivatives active against HIV

We report for the first time the application of chlorofullerene C60Cl6 as a substrate for straightforward preparation of highly water-soluble fullerene derivatives, promising compounds for investigation of the biological action of fullerenes in vitro and in vivo. Methyl esters of phenylacetic and benzylmalonic acids were used as reagents in the Friedel-Crafts arylation of C60Cl6 that resulted in the corresponding C60(Ar)5Cl compounds with 50-60% yields. The following cleavage of ester groups in phenylacetic and benzylmalonic residues was accomplished almost quantitatively to yield the corresponding fullerene-based acids bearing 5 and 10 carboxylic groups, respectively. The relatively-low solubility of these acids in water can be strongly enhanced (up to 150-200 mg ml(-1)) by their conversion to salts with alkali metal cations. These fullerene salt derivatives showed pronounced anti-HIV action and low toxicity; these two findings point to the necessity for further investigation of the biological properties of the here-reported compounds.     

The First Mixed-Halide Zirconium Cluster Compounds: Zr(6)Cl(1.6)I(10.4)Be, Zr(6)Cl(1.3)I(10.7)B, and Zr(6)Cl(11.5)I(1.5)B. Matrix Effects and Halogen Substitution in Compact Network Structures

Investigations of the effect of halogen size on structure stability have been conducted in well-reduced and heavily interbridged zirconium chloride-iodide cluster systems. The title compounds are obtained in good yields from reactions of Zr, ZrCl(4), ZrI(4), and B or Be in sealed Ta tubes for approximately 4 weeks at 850 degrees C. Single-crystal diffraction at room temperature established these as Zr(6)Cl(1.65(4))I(10.35(4))Be and Zr(6)Cl(1.27(3))I(10.73(3))B [R&thremacr;, Z = 3, a = 14.3508(8), 14.389(1) ?, c = 9.8777(9), 9.915(2) ?, respectively] and Zr(6)Cl(11.47(2))I(1.53(2))B [P4(2)/mnm, Z = 2, a = 12.030(1) ?, c = 7.4991(8) ?]. These are derivatives of the Zr(6)I(12)C and orthorhombic Zr(6)Cl(13)B structures, respectively, the latter containing unusual linear chains of clusters interbridged by Cl(i-i) that are in turn interconnected by three-bonded Cl(a-a-a) atoms. The random substitution of fractional Cl at specific I sites in the first two, and I for certain Cl in the third, was positionally resolved in all cases. The replacement always occurs at two-bonded X(i), so that single types of halogen are left in sites that interconnect clusters and generate the three-dimensional array. Structural changes seen in both structures are specifically related to relief of X.X crowding in the parent structure (matrix effects). Substitution of Cl for I(i) in the Zr(6)I(12)C type greatly reduces intercluster I.I repulsions and allows, among other things, a 0.20 ? (5.8%) reduction in Zr-I(a-i) intercluster bond lengths. Increased Cl.I repulsions caused by I substitution in orthorhombic Zr(6)Cl(13)B (Pnnm) convert the twisted chains and angular Cl(a-a-a) interchain bridges to planarity in tetragonal Zr(6)Cl(11.5)I(1.5)B. Phase widths found are 0 相似文献   

1,3-二(2,6-二甲基苯基)-2-四氢咪唑基-苯亚甲基-二吡啶基-二氯合钌化合物的合成

设计了由1,3-二(2,6-二甲基苯基)-2-四氢咪唑基-苯亚甲基-三苯基膦-二氯合钌(7)和吡啶反应生成无膦型金属钌卡宾化合物1,3-二(2,6-二甲苯基)-2-四氢咪唑基-苯亚甲基-2-吡啶基-二氯合钌(8),8作为高效催化剂用于丙烯腈和烯丙基苯的交叉交互置换反应.新化合物7,8经核磁共振氢谱、碳谱和高分辨率质谱予以证实.