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1.
The heat capacities of benzoylferrocene (BOF), C 5H 5FeC 5H 4COC 6H 5, and benzylferrocene (BF), C 5H 5FeC 5H 4CH 2C 6H 5, have been measured by the low-temperature adiabatic calorimetry in the temperature range from 6 K to 372 K. The purity benzylferrocene and thermodynamic properties – the triple point temperature and the enthalpy of fusion have been obtained. The ideal gas thermodynamic functions (changes of the entropy, enthalpy, and Gibbs free energy) of BOF and BF were derived at T = 298.15 K using the heat capacities and previously determined data on the saturation vapours pressures and the enthalpies of sublimation. The ideal gas enthalpy of formation and absolute entropy of BOF at T = 298.15 K have been obtained from quantum chemical calculations, where as the thermodynamic properties of BF have been estimated by empirical method of group equations. A good agreement between experimental and theoretical values provides an additional check of the reliability of the experimental data. 相似文献
2.
The heat capacity of iso-butylferrocene C 5H 5FeC 5H 4-C 4H 9- i was measured over the temperature range 7–372 K in an adiabatic vacuum calorimeter. Substance purity and the thermodynamic
characteristics of fusion (temperature, enthalpy, and entropy) were determined. Saturated vapor pressures and the enthalpies
of vaporization of n-propylferrocene C 5H 5FeC 5H 4-C 3H 7- n, propionylferrocene C 5H 5FeC 5H 4-COC 2H 5, and iso-butylferrocene were measured by the dynamic method of substance transfer in an inert gas flow. The entropy, enthalpy, and
Gibbs energy of the substances in the ideal gas state at 298.15 K were calculated. The thermodynamic values obtained in this
work and reported in the literature for ferrocene alkyl and acyl derivatives were critically analyzed. The mutual consistency
of the data on both homologous series was checked. 相似文献
3.
A series of arylantimony ferrocenecarboxylates with the formula (C 5H 5FeC 5H 4CO 2) nSbAr (5?n) ( n = 1, 2; Ar = C 6H 5, 4‐CH 3C 6H 4, 3‐CH 3C 6H 4, 2‐CH 3C 6H 4, 4‐ClC 6H 4, 4‐FC 6H 4) were synthesized and characterized by elemental analysis, IR, 1H NMR and mass spectra. The crystal structures of (C 5H 5FeC 5H 4CO 2) 2Sb(4‐CH 3C 6H 4) 3 and C 5H 5FeC 5H 4CO 2SbPh 4 were determined by X‐ray diffraction. Four human neoplastic cell lines (HL‐60, Bel‐7402, KB and Hela) were used to screen these compounds. The results indicate that these compounds at 10 µM show certain in vitro antitumor activities. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
4.
The heat capacity ( C p, m) of ferrocenemethanol (FM) C 5H 5FeC 5H 4CH 2OH have been measured by the low-temperature adiabatic calorimetry method in the range 6–371 K. The triple point temperature, the enthalpy of fusion, and the purity of the substance under consideration have been determined. The ideal gas thermodynamic functions of FM—absolute entropy S m(g) 0 and change in the enthalpy Δ 0 T H m at 298.15 K—have been derived from the heat capacity data and the known values of the saturation vapor pressure and enthalpy of sublimation. The ideal gas thermodynamic functions C p, m 0 and S m(g) 0 and the enthalpy of formation of FM have been calculated by the empirical difference method at T = 298.15 K. The experimental and calculated values of the thermodynamic functions are consistent within error limits, which proves their reliability. 相似文献
5.
The enthalpies of fusion of C 6H 5SiH 3, C 6F 5Si(CH 3) 3, and (C 6H 5) 4Si were obtained in scanning calorimetry measurements. Pressure over the condensed talylsilane 4-CF 3C 6F 4SiCH 3, phenylsilane C 6H 5SiH 3, and pentafluorophenylsilane C 6F 5SiCH 3, (C 6F 5) 2Si(CH 3) 2, and (C 6F 5) 4Si phases was measured by the static method with the use of membrane null manometers. Equations approximating the dependences of saturated vapor pressures on temperature and the enthalpy and entropy of vaporization were obtained. 相似文献
6.
In the present research, the temperature dependence of heat capacity of tris(pentafluorophenyl)-4-pyridylethylgermane (C6F5)3Ge–CH2–CH2–C5H4N was studied by precise adiabatic vacuum calorimetry and differential scanning calorimetry over the temperature range from 6 to 450 K. The temperature and enthalpy of fusion of tris(pentafluorophenyl)-4-pyridylethylgermane and the total mole fraction of impurities have been determined. The thermal stability of the sample was investigated by thermogravimetric analysis. The experimental data were used to calculate the standard thermodynamic functions: heat capacity, enthalpy, entropy, and the Gibbs energy over the range from T → 0 to 420 K for crystalline and liquid states. For the compound under study, the standard entropy of formation in the crystalline state was calculated at T = 298.15 K. In addition, the structure of the investigated compound was established, and corresponding structural parameters were determined. 相似文献
7.
Oxidation of exo-substituted (cyclohexadienyl)cyclopentadienyliron derivatives, exo-RC 6H 6FeC 5H 5 (R = C 2H 5, C 6H 5CH 2 or C 5H 5), by (Ph 3C)BF 4 or bromosuccinimide proceeds by either of two routes, exo-R abstraction or endoH abstraction. Mixtures of [C 6H 6FeC 5H 5] + and [RC 6H 5FeC 5H 5] + axe formed in the reactions. The tendency for R-abstraction rises along the series C 5H 5 C 2H 5 < C 6H 5CH 2. When heated, the compounds (arene H) FeC 5H 5 axe transformed to ferrocene. 相似文献
8.
Binuclear complexes of formula C 5H 15FeC 5H 4COOSn(CHCH 2) 3 (I), C 5H 5FeC 5H 4COOSnPh 3 (II) and Ph 3GeCOOSnPh 3 (III) have been prepared and characterized by IR spectra. The polymeric structure of solid C 5H 5FeC 5H 4COOSn(CHCH 2) 3 has been established by X-ray crystallography. The crystals are monoclinic, space group P2 1/ a, with a 15.105(5), b 10.030(4), c 11.402(4) Å, and β 104.06(4)°. In this compound the tin atoms are five-coordinate trigonal bipiramidal, with the vinyl groups equatorial and two apical oxygen atoms from bridging carboxylato groups. The resulting structure is a linear polymer with SnO bond lengths of 2.12 and 2.42 Å. The spectra indicate that similar polymeric structure exist also for compounds II and III in the solid state, whereas an equilibrium monomer ? dimer seems to be present in CHCl 3 solution for the compound III. 相似文献
9.
Quantum-chemical calculations of ferrocenylmethyl ([C 5H 5FeC 5H 4CH 2] +) and ferrocenylenedimethyl ([C 5H 5FeC 5H 3(CH 2) 2] 2+) cations with full geometry optimization were carried out using the Hartree—Fock (HF) approximation, density functional theory (DFT), and at the second-order Møller—Plesset (MP2) level of perturbation theory in the 6-311G* basis set. The methods with inclusion of electron correlation in explicit form indicate that the CH 2groups deviate from the cyclopentadienyl ring planes toward the Fe atom due to formation of the Fe—CH 2bonds. According to Hartree—Fock calculations, ligands in these ions are virtually planar. The metallonium character of the ions studied was demonstrated based on the results of analysis of the electron density distribution and frontier orbitals. 相似文献
10.
The Bi 2Fe 2(C 2O 4) 5·5H 2O was synthesized by solid-state reaction at low heat using Bi(NO 3) 3·5H 2O, FeSO 4·7H 2O, and Na 2C 2O 4 as raw materials. The nanocrystalline BiFeO 3 was obtained by calcining Bi 2Fe 2(C 2O 4) 5·5H 2O at 600 °C in air. The precursor and its calcined products were characterized by thermogravimetry and differential scanning calorimetry, FT-IR, X-ray powder diffraction, and vibrating sample magnetometer. The data showed that highly crystallized BiFeO 3 with hexagonal structure [space group R3c(161)] was obtained when the precursor was calcined at 600 °C in air for 1.5 h. The thermal process of the precursor in air experienced five steps which involved, at first, the dehydration of an adsorption water molecule, then dehydration of four crystal water molecules, decomposition of FeC 2O 4 into Fe 2O 3, decomposition of Bi 2(C 2O 4) 3 into Bi 2O 3, and at last, reaction of Bi 2O 3 and Fe 2O 3 into hexagonal BiFeO 3. Based on Starink equation, the values of the activation energies associated with the thermal process of Bi 2Fe 2(C 2O 4) 5·5H 2O were determined. Besides, the most probable mechanism functions and thermodynamic functions (Δ S ≠, Δ H ≠, and Δ G ≠) of thermal processes of Bi 2Fe 2(C 2O 4) 5·5H 2O were also determined. 相似文献
11.
Symmetrical and asymmetrical triphenylene discotic liquid crystals with two kinds of different peripheral chains, sym-TP(OC 11H 23) 3(O 2CR) 3 and asym-TP(OC 11H 23) 3(O 2CR) 3, (R=CH 2OC 2H 5, CH 2OC 3H 7, CH 2OC 4H 9, CH 2OC 5H 11, C 3H 7, C 4H 9, C 5H 11, C 6H 13, C 7H 15) were synthesized. Their thermotropic liquid crystalline properties were studied by polarizing optical microscopy (POM) and
differential scanning calorimetry (DSC). The results showed that the asymmetrical compounds had higher melting and clearing
points than that of their corresponding symmetrical compounds. For the same series of compounds, TP(OC 11H 23) 3(O 2CR) 3, their melting points decrease and clearing points increase gradually with the lengthening of ester chains. Most of the β-oxygen
containing esters of triphenylene derivatives, TP (OC 11H 23) 3(O 2CR) 3, (R=CH 2OC 2H 5, CH 2OC 3H 7, CH 2OC 4H 9, CH 2OC 5H 11), symmetrically or asymmetrically attached on triphenylene cores, have higher melting and clearing points than those of triphenylene
derivatives, TP(OC 11H 23) 3(O 2CR) 3, (R=C 4H 9, C 5H 11, C 6H 13, C 7H 15), with the same length of peripheral chains. The triphenylene derivatives with longer peripheral chains have shown mesophase
at room temperature.
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Translated from Chemical Research and Application, 2007, 19(10) (in Chinese) 相似文献
12.
The reaction of ferrocenylacetylide compounds with Co 2(CO) 8 at room temperature affords four complexes bearing ferrocenyl units with approximately tetrahedral (μ-alkyne)dicobalt moieties [R–(C≡C) n –R′] [Co 2(CO) 6] n ′ [R?=?C 5H 5FeC 5H 4-C(CH 3) 2-C 5H 4FeC 5H 4, R′?=?H, n?=?1, n′?=?1 ( 1); R?=?C 5H 5FeC 5H 4 [ferrocenyl (Fc)], R′?=?–CH=CHCl, n?=?1, n′?=?1 ( 2); R?=?Fc, R′?=?Fc, n?=?2, n′?=?1 ( 3), n′?=?2 ( 4)]. The compounds were characterized by elemental analysis, IR, 1H( 13C) NMR, MS and single-crystal X-ray diffraction analysis. The X-ray analyses show that coordination of the carbon–carbon triple bond and the dicobalt unit result in the formation of a Co 2C 2 tetrahedral core, and the substituents on the acetylenic units show a distortion from linearity that reflects this coordination mode. 相似文献
14.
A gas-chromatographic procedure was developed for determining impurities (CH 4, C 2H 6, C 3H 8, C 4H 10, iso-C 4H 10, C 5H 12, iso-C 5H 12, neo-C 5H 12, CH 3Cl, C 2H 5Cl, CH 2Cl 2, CHCl 3, CO, and CO 2) in hydrogen chloride using two columns and a column switching technique in an isothermal mode with a flame ionization detector;
the detection limits were 0.01–0.1 ppm. The matrix was separated in a precolumn packed with urea. CO and CO 2 were determined by reaction gas chromatography with their conversion into methane. 相似文献
15.
Synthetic routes for the preparation of 3-alkyl-6-phenyl-4( 3H)-pteridinones 6 and their corresponding 8-oxides 5 (R = CH 3, C 2H 5, (CH 2) 2CH 3, (CH 2) 3CH 3, CH(CH 3)C 2H 5, CH(CH 3) 2 and CH(C 2H 5)CH 2OCH(OC 2H 5) 2 are described and their reactivities towards xanthine oxidase from Arthrobacter M-4 are determined. Only the 3-methyl derivative of 6-phenyl-4( 3H)-pteridinone and its 8-oxide i. e. 6a and 5a are found to be substrates although their reactivities are still very low. Oxidation takes place at C-2 of the pteridinone nucleus. All the 3-alkyl derivatives are less tightly bound to the enzyme than 6-phenyl-4( 3H)-pteridinone. Introduction of the N-oxide at N-8 considerably lowers the binding of the substrates. Inhibition studies have revealed that 3-methyl-6-phenyl-4( 3H)-pteridinone ( 6a ) is a non-competitive inhibitor with a Ki-value of 47 μM and the 3-ethyl derivative ( 6b ) an uncompetitive one with a Ki-value of 19.6 μM. 相似文献
16.
The kinetics of conversion of ozone complexes with a series of substituted benzene ArX.O 3 (ArX=C 6H 5CH 3, C 6H 5C 2H 5, C 6H 5CH(CH 3) 2, C 6H 5C(CH 3) 3, C 6H 5F, C 6H 5Cl, m-BrC 6H 4CH 3, C 6H 5CH 2Cl have been studied by spectrophotometry. The rate of ArX.O 3 consumption in CH 2Cl 2-ArX solutionis W=k 0 [ArX. O 3]+k 1 [ArX. O 3] [ArX]. 相似文献
17.
Reactions of Fe + and FeL + [L=O, C 4H 6, c-C 5H 6, C 5H 5, C 6H 6, C 5H 4(=CH 2)] with thiophene, furan, and pyrrole in the gas phase by using Fourier transform mass spectrometry are described. Fe +, Fe(C 5H 5) +, and FeC 6H 6 + yield exclusive rapid adduct formation with thiophene, furan, and pyrrole. In addition, the iron-diene complexes [FeC 4H 6 + and Fe( c-C 5H 6) +], as well as FeC 5H 4(=CH 2) + and FeO +, are quite reactive. The most intriguing reaction is the predominant direct extrusion of CO from furan by FeC 4H 6 +, Fe( c-C 5H 6) +, and FeC 5H 4(=CH 2) +. In addition, FeC 4H 6 + and Fe( c-C 5H 6) + cause minor amounts of HCN extrusion from pyrrole. Mechanisms are presented for these CO and HCN extrusion reactions. The absence of CS elimination from thiophene may be due to the higher energy requirements than those for CO extrusion from furan or HCN extrusion from pyrrole. The dominant reaction channel for reaction of Fe( c-C 5H 6) + with pyrrole and thiophene is hydrogen-atom displacement, which implies D O(Fa(N 5H 5) +-C 4H 4X)>D O(Fe(C 5H 5) +-H)=46±5 kcal mol ?1. D O(Fe +-C 4H 4S) and D O(Fe +-C 4H 5N)=D O(Fe +-C 4H 6)=48±5 kcal mol ?1. Finally, 55±5 kcal mol ?1=D O(Fe +-C 6H 6)>D O(Fe +-C 4H 4O)>D O(Fe +-C 2H 4)=39.9±1.4 kcal mol ?1. FeO + reacts rapidly with thiophene, furan, and pyrrole to yield initial loss of CO followed by additional neutral losses. D O(Fe +-CS)>D O(Fe +-C 4H 4S)≈48±5 kcal mol ?1 and D O(Fe +-C 4H 5N)≈48±5 kcal mol ?1>D O(Fe +-HCN)>D O(Fe +-C 2H 4)=39.9±1.4 kcal mil ?1. 相似文献
18.
Mass spectra of substituted benchrotrenyls RC 6H 5Cr(CO) 3 where R?H, F, CI, I, CH 3, OCH 3, COOCH 3, C 2H 5, N(CH 3) 2, NH 2, C 6H 5, C(CH 3) 3, p-C 6H 4NH 2, CH 2C 6H 5, CH 2CH 2C 6H 5), 1,3,5-(CH 3) 3C 6H 3Cr(CO) 3 and 1,2,3,5-(CH 3) 4C 6H 2Cr(CO) 3 have been studied. It has been found that for monosubstituted benchrotrenyls there is a linear dependence of the parameter log [Cr] +/[RC 6H 5Cr] +) on the number of degrees of freedom of the [RC 6H 5Cr] + ion. Decarbonylation of the molecular ions is not affected by the nature of the substituent R. The results are interpreted in terms of the quasi-equilibrium theory of mass spectra. 相似文献
19.
The reaction of LnCl 3· xTHF with Na(C 5H 4CH 2CH 2PPh 2) followed by the in situ reaction with Na 2(C 14H 10) afforded the (C 5H 4CH 2CH 2PPh 2)Ln(C 14H 10)L complexes (Ln = Y or Lu and L = THF or DME). The structure of (C 5H 4CH 2CH 2PPh 2)Lu(C 14H 10)(DME) was established by X-ray diffraction. In solution, there is an equilibrium between the complexes with the coordinated
and uncoordinated phosphorus atom.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1687–1689, September, 2007. 相似文献
20.
Cyclopentadienyl cobalt complexes (η 5‐C 5H 4R) CoLI 2 [L = CO,R=‐COOCH 2CH=CH 2 (3); L=PPh 3, R=‐COOCH 2‐CH=CH 2 (6); L=P(p‐C 6H 4O 3) 3, R = ‐COOC(CH 3) = CH 2 (7), ‐COOCH 2C 6H 5 (8), ‐COOCH 2CH = CH 2 (9)] were prepared and characterized by elemental analyses, 1H NMR, ER and UV‐vis spectra. The reaction of complexes (η 5‐C 5H 4R)CoLI 2 [L= CO, R= ‐COOC(CH 3) = CH 2 (1), ‐COOCH 2C 6H 5(2); L=PPh 3, R=‐COOC (CH 3) = CH 2 (4), ‐COOCH 2C 6H 5 (5)] with Na‐Hg resulted in the formation of their corresponding substituted cobaltocene (η 5‐C 5H 4R) 2 Co[R=‐COOC(CH 3) = CH 2 (10), ‐COOCH 2C 6H 5 (11)]. The electrochemical properties of these complexes 1–11 were studied by cyclic voltammetry. It was found that as the ligand (L) of the cobalt (III) complexes changing from CO to PPh 3 and P( p‐tolyl) 3, their oxidation potentials increased gradually. The cyclic voltammetry of α,α′‐substituted cobaltocene showed reversible oxidation of one electron process. 相似文献
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