One isomer of C60(i-C3F7)8, three isomers of C60(i-C3F7)6, and the first mixed perfluoroalkylated fullerene, C60(CF3)2(i-C3F7)2, have been isolated by HPLC from a mixture prepared by reaction of C60 with heptafluoroisopropyl iodide in a glass ampoule at 260-290 °C. The molecular structures of the four new compounds have been determined by means of X-ray single crystal diffraction partially also by use of synchrotron radiation. Theoretical calculations at the DFT level of theory have been employed to rationalize the energetics of isomers and of C60-Rf binding. 相似文献
The high temperature reaction of C60 with silver(I) trifluoroacetate followed by 500 °C sublimation and subsequent HPLC purification has led to the isolation of the five trifluoromethyl[60]fullerenes C60(CF3)n (n=2, 4, 6, 8, 10). Four of them have >90% compositional purity. Two of the compounds, C60(CF3)4 and C60(CF3)6, were obtained as C1-symmetry isomers with >90% isomeric purity, and a sample of C60(CF3)2 also contained ca. 15-20% of a Cs-symmetry isomer of C60(CF3)4. The new compounds were characterized by IR and EI mass spectrometry (all five compounds), NMR spectroscopy (C60(CF3)2, C60(CF3)4, and C60(CF3)6), and 2D COSY NMR spectroscopy (C60(CF3)4 and C60(CF3)6). Calculations at the AM1 and DFT levels of theory have led to the prediction of the most likely structures for C60(CF3)2, C1-C60(CF3)4, Cs-C60(CF3)4, and the two most likely structures of C1-C60(CF3)6. 相似文献
A novel isomer of C70(CF3)6 has been isolated by HPLC from a mixture prepared by trifluoromethylation of C70 with CF3COOAg. The X-ray structure revealed an unprecedented arrangement of CF3 groups forming a p3mp ribbon. This result provides additional evidence of the preferable formation of trifluoromethylated fullerene molecules comprising a single continuous ribbon of edge-sharing para- and meta-C6(CF3)2 hexagons. 相似文献
Cleavage of the E-P bond in compounds of the type (CF3)2EPh2(E = P, As) is achieved by polar [HBr, (CF3)2EI, (CH3)3SnH, (CF3)2AsH] and non-polar [Br2, Mn2(CO)10] substances. Exchange reactions are possible with (CF34)E2 and P2F4 leading to the unsymmetrical compounds (CF3)2PPF2, (CF3)2AsPF2, (CF3)2PAs(CF3)2, F2PPH2, (CF3)2AsPH2. The reaction of (CF3)2PPH2 with Mn2(CO)10 gives the new binuclear complex Mn2(CO)8PH2P(CF3)2 and Mn2(CO)8[P(CF3)2]2. The hitherto unknown compound (CF3)2AsPF2 is obtained by the reaction of (CF3)2AsPH2 with P2F4. Adducts of (CF3)2PPH2 with B2H6 and (CH3)3N, respectively, are discussed. Investigation of the reaction route and characterization of most of the reaction product is based on 1H and 19F NMR spectral data. 相似文献
Ampoule reactions of C70 with n- and i-C3F7I were carried out at 250-310 °C. Two step HPLC separations allowed the isolation of several C70(n-C3F7)4-8 and C70(i-C3F7)4 compounds. Crystal and molecular structures of C70(n-C3F7)8-V, C70(n-C3F7)6O, C70(n-C3F7)4, and three isomers of C70(i-C3F7)4 have been determined by X-ray crystallography using synchrotron radiation. Molecular structures of the new compounds were compared with the known examples and discussed in terms of addition patterns and relative energies of their formation. 相似文献
Ab initio calculations employing an extended 4-31G basis set have been applied to the highly fluorinated molecules, CF3O2H, CF3O2F and CF2(OF)2. Partial geometry optimizations have also been carried out on these molecules allowing a comparison between theory and the recently completed gas-phase electron diffraction results. The O-O bond distance in CF3O2 H is found to be longer (by 0.02 Å) than the corresponding bond in CF3O2F while the CO bond is found to be shorter (by 0.02 Å) in CF3O2H. The OF bond in CF3O2F is found to be longer (by 0.03–0.04 Å) than the corresponding bond in CF3OF or F2O. Torsional barriers have been computed for CF3O2H and CF3O2F with the aid of Fourier analysis of the potential curves. CF3O2H is found to have a torsional potential about the peroxide bond rather similar to that found for H2O2 while in CF3O2F the cis and trans barriers are predicted to be much larger (14.6 and 8.4 kcal mol?1, respectively). The threefold barrier to rotation of the CF3 group in CF3O2F is predicted to be 4.4 kcal mol?1. Various conformations of CF2(OF)2 have also been studied with conformations consistent with the operation of the gauche-effect being most stable. Bond separation energies and molecular properties have also been computed for these molecules. 相似文献
The fluorocarbon soluble, binuclear ruthenium(I) complexes [Ru(μ-O2CMe)(CO)2LF]2, where LF is the perfluoroalkyl substituted tertiary phosphine, P(C6H4-4-CH2CH2(CF2)7CF3)3, or P(CH2CH2(CF2)5CF3)3, were synthesized and partition coefficients for the complexes in fluorocarbon/hydrocarbon biphases were determined. Catalytic hydrogenation of acetophenone to 1-phenylethanol in benzotrifluoride at 105 °C occured in the presence of either [Ru(μ-O2CMe)(CO)2P(C6H4-4-CH2CH2(CF2)7CF3)3]2 (1) or [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2 (2). The X-ray crystal structure of [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2 was determined. The compound exhibited discrete regions of fluorous and non-fluorous packing. 相似文献
The title compound (1) was prepared by the reaction of 3,5-bis(CF3)C6H3P(i-C3H7)2 (L1) and Co2(CO)8. Its solubility in supercritical carbon dioxide was measured at varying temperatures and pressures using a modified analytical extraction device. Solubility data were determined in the temperature and pressure ranges between 40 and 70 °C and between 100 and 300 bar, respectively. The solubility of 1 is lower compared to (p-CF3C6H4)3P, but much higher than for transition metal complexes bearing phosphines without fluorinated substituents. 相似文献
The trifluoromethylation reactions of (CF3)2Hg, CF3I and (CF3)2Te with cyclohexene, benzene and pyridine are compared under similar conditions. Photochemical as well as thermal reactions result in an increase of the reactivity in the series (CF3)2Hg < CF3I ? (CF3)2Te. The yields and the kind of products vary depending on the time of irradiation and the temperature. In all cases the best yields are obtained from the thermal reactions with (CF3)2Te. With cyclohexene only trifluoromethylated addition products are observed. The substitution reactions with pyridine yield a mixture of isomeric trifluoromethylpyridines. (CF3)2Hg and CF3I react with benzene to yield only benzotrifluoride C6H5CF3. The main product of the reaction of (CF3)2Te with benzene is also benzotrifluoride; in addition to this the disubstituted bis(trifluoromethyl)benzene isomers and trifluoromethyl- cyclohexadienes are formed. 1H, 19F n.m.r. and mass spectra are described. 相似文献
Spectral analysis of the CF2(1B1) → CF2(1A1) transition showed that the energy distribution found in the v2 bending vibration (v'2 ? 3) of CF2(1B1) produced from the triplet-triplet annihilation of CF2(3B1) and from the vacuum ultraviolet photolysis of C2F4 are approximately statistical and closely related to each other. 相似文献
The 193 nm laser photodissociation of CH2H2 and CF3C2H has been studied. With the laser beam focused, C2(d3Πg) and CH(A2Δ) radicals were formed by multiphoton processes in both C2H2 and CF3C2H; however, the one-photon process forming C2H is still predominant in CF3C2H photolysis. The production of C2(d3Πg) and CH(A2Δ) emissions is prompt,and the emission intensities show similar (less than quadratic) dependence on laser power whether the radicals are produced from C2H2 or CF3C2H. In addition, the vibrational distribution of the Swan system is nearly the same in CF3C2H as in C2H2. The results indicate that the overall photolytic processes are similar in two molecules. Both the C2(d3Πg) and CH(A2Δ) emissions are quenched by Xe with rate constants of 4.8×10?11 and 1.8×10?11 cm3 molecule?1 s?1, respectively. 相似文献
A new method for the preparation of bis(perfluoroorgano) zinc compounds is described: CF3I and C6F5I react with dialkylzinc in the presence of a Lewis base quantitatively to give (CF3)2Zn and (C6F5)2Zn complexes, while the analogous reactions with C2F5I and iC3F7I do not yield the pure compounds. 1H, 19F n.m.r, i.r. and Raman spectra are presented. 相似文献
Fluorination of C60(s), C60(s)-MnF2(s), C60(s)-NiF2(s) and C60(s)-MnF3(s) mixtures has been studied by Knudsen cell mass spectrometry with admission of molecular fluorine. The fluorination is selective when fullerene reacts with the fluorine chemisorbed on the MnF2 surface. When the MnF2 content in the initial mixture is at least 90 mol% both C60F18 and C60F36 are selectively formed. Under certain conditions, mixtures predominantly containing one of three compounds C60F38, C60F40, and C60F42 can be obtained. A consecutive change of the main fluorination products (C60F18 and C60F36) takes place at constant temperature (720 K) and on fluorine admission. A quantitative explanation of this fact is given. Selective fluorination of C60(s) by molecular fluorine is compared with solid-phase fluorination using MnF3(s) as a fluorinating agent. 相似文献
The insertion of (CF3)2CO into the PH bond of MenH3?nP yields MenH2?nPC(CF3)2OH and MenH1?nP[C(CF3)2OH]2 (n=O, 1), respectively [1]. MeP[C(CF3)2OH]2 rearranges giving the diphosphine [MePOCH(CF3)2]2 and the phosphorane MeP[OCH(CF3)2]4. Me2PH reacts with (CF3)2CO forming several products, e.g. MePF[OCH(CF3)2]2 and Me2PPMe2 [1]. The phosphines tBu(R)PH(R=Me, tBu), however, add (CF3)2CO giving rise to the phosphinites tBu(R)POCH(CF3)2, which furnish stable phosphonium salts upon treating with MeI. (CF3)2CO inserts into the SH bond of RSH to yield RSC(CF3)2OH (R=H,Me,Ph), which were reacted with MeI, too. Reacting SCl2 with LiOCH(CF3)2 gives S[OCH(CF3)2]2 which is oxidised by chlorine to the sulfurane ClS[OCH(CF3)2]3 [2]. The sulfurane is able to transfer (CF3)2CHO groups to phosphorus (III) compounds, e.g. P[OCH(CF3)2]3 and Me3P yielding P[OCH(CF3)2]5 and [Me3POCH(CF3)2]+Cl?. ClS[OCH(CF3)2]3 gives a stable salt upon reaction with SbCl5, like ClP[OCH(CF3)2]4. The mechanisms for these reactions are discussed. 相似文献
It has been found that a mixture of (CF3SO2)2CH2 and (CF3SO2)2CBr2 can be used instead of (CF3SO2)2CHBr in the radical addition to H2CCF2; the 1:1 and 1:2 adducts have been isolated and characterized. An improved synthesis of (CF3SO2)2CBr2 is also reported. 相似文献
The reactions of M(CO)5X ( M = Mn, Re; X = Cl, Br, I) with E2(CF3)4 (E = P, As) between 50 and 90°C yield binuclear complexes of the type M2(CO)8E(CF3)2X with two different bridging ligands, the formation of which is influenced by M (Mn > Re), E (P > As) , and X(I > Br > Cl). The main by-product is the symmetrical system M2(CO)8[E(CF3)2]2, which is however not formed by the partial replacement of X by E(CF3)2 since this reaction requires temperatures above 120°C. The observed products can be explained by a three-step reaction path starting with the cleavage of E2(CF3)4 followed by the subtitution of a cis-CO group in the M(CO)5X component by M(CO)5E(CF3)2 and the ring closure. 相似文献
Reactions of the fluorinated amines (CF3)2NH, CF3N(OCF3)H, CF3N[OCF(CF3)2]H, CF3NHF and SF5NHF with the strong acid HF/AsF5 form the corresponding ammonium salts Rf1Rf2NH2+AsF6? and RfNFH2+ AsF6? in high yield. [Rf1=CF3, Rf2=CF3, CF3O, (CF3)2CFO; Rf=CF3, SF5] The colorless crystalline solids are stable for prolonged periods at 22°C in sealed FEP containers. They have dissociation pressures at 22°C ranging from ～5 torr (RfNFH2+ AsF6?) to ～50 torr [CF3N(OCF3)H2+AsF6?]. 19F NMR and Raman spectroscopy were used to identify the compounds. 相似文献
New experimental results on perfluoroalkylation of C60 and C70 with the use of RfI (Rf = CF3, C2F5, n-C3F7, n-C4F9, and n-C6F13), along with a critical overview of the existing synthetic methods, are presented. For the selected new fullerene (Rf)n compounds we report spectroscopic, electrochemical and structural data, including improved crystallographic data for the isomers of C70(C2F5)10 and C60(C2F5)10, and the first X-ray structural data for the dodecasubstituted perfluoethylated C70 fullerene, C70(C2F5)12, which possesses unprecedented addition pattern. 相似文献
Trifluoronitrosomethane reacts with bis(trifluoromethyl)phosphine to give (CF3)2P(O)N(OH)CF3 and a small amount of (CF3)2NOH. On the other hand, the reactions with tris(trifluoromethyl)phosphine and bis(trifluoromethyl)chlorophosphine afford (CF3)2NOP(O)CF3N(CF3)2 and (CF3)2NP(O)(CF3)Cl respectively. Isomerisation of may be involved as found for the isomerisation of the phosphine, (CF3)2NOP(CF3)2, to the phosphoryl compound, (CF3)2NP(O)(CF3)2. Mechanisms for the above reactions are discussed. 相似文献
Enthalpies of formation of ground states of the gaseous particles CF, CF2, C2F5, CF4, CF3I, C2F4, and C2F6 were calculated by ab initio method in the CCSD(T) approximation with extrapolation to the full basis and regard to the correlation energy. Their equilibrium geometrics, frequencies
of normal vibrations, and other values were found by the B3LYP/aug-cc-pvdz method, from which thermodynamic functions within
the range of 0–6000 K were calculated. Equilibrium constants were calculated from these functions, and then the information
on the rate constants in the limit of high pressures was obtained. 相似文献
