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1.
Aqua magnesium phthalocyanine bis(diethylamine) complex was obtained in the crystalline form and its crystal structure was determined by single-crystal X-ray diffraction. The Mg atom is 4 + 1 coordinated by four N isoindole atoms and one O atom. The MgPc moiety is non-planar, the Mg(II) is deviated by 0.492(2) Å from the N4-isoindole plane towards the oxygen atom of water molecule. The arrangement of MgPc(H2O) and diethylamine molecules is determined by O–HN hydrogen bonds and π–π interactions. The complex is stable up to 140 °C. At this temperature the complex loses diethylamine molecules and next at 200 °C loses the water molecule and finally converts into β-MgPc.  相似文献   

2.
Isochoric PVTx measurements have been performed for the binary system of nitrous oxide + CH3F (R41), +CH2F2 (R32), and +CHF3 (R23) using a new experimental set-up. The experiments covered both the two-phase region and the superheated vapor region and were performed within the temperature range 214–358 K and within a pressure range from 270 to 5600 kPa. Data have been collected for not less than four compositions for each system. The vapor–liquid equilibrium data were derived correlating the experimental data by means of the Carnahan–Starling–De Santis equation of state. The studied systems show a positive deviation from the Raoult's law. The results obtained were compared with the Burnett PVTx data. The two methods showed a mutual consistency within an acceptable margin of error. No other experimental PVTx data were found in the literature for these binary systems.  相似文献   

3.
Liquid–liquid equilibrium (LLE) data of water + acetic acid + dimethyl adipate have been determined experimentally at 298.15, 308.15 and 318.15 K. Complete phase diagrams were obtained by determining binodal curve and tie-lines. The reliability of the experimental tie-line data was confirmed by using the Othmer-Tobias correlation. UNIFAC and modified UNIFAC models were used to predict the phase equilibrium in the system using the interaction parameters determined from experimental data of CH2, CH3COO, CH3, COOH, and H2O functional groups. Distribution coefficients and separation factors were evaluated for the immiscibility region.  相似文献   

4.
Solubility measurements of sulfur compounds in supercritical fluids are required in order to determine the feasibility of supercritical extraction for removing them from gasoline and diesel fuel. In this work, solubility of thiophene in CO2 and in CO2 + 1-propanol mixtures were measured from 313 to 363 K using an apparatus based on the static–analytical method. Vapor–liquid equilibria (VLE) data of binary mixtures were fitted to the Peng–Robinson equation of state (EoS) with classical mixing rules. The binary interaction parameters (kij) obtained were used to predict the VLE data of ternary systems. The calculated values given by this simple model agree well to the experimental data.  相似文献   

5.
Vapor–liquid equilibria (VLE), vapor–liquid–liquid equilibria (VLLE) and critical point (CP) data for the carbon dioxide+1-hexanol (at 324.56, 353.93, 397.78, 403.39, 431.82 and 432.45 K up to 20 MPa) and carbon dioxide+1-heptanol (at 313.14, 333.16, 373.32, 411.99 and 431.54 K up to 21 MPa) systems are reported. Phase behavior measurements were made in a new equilibrium cell based on the static-analytic method and capable of measurements up to 60 MPa and 673 K. The Peng–Robinson equation of state (EoS) with the Wong–Sandler mixing rules and temperature independent parameters was able to correlate and extrapolate the VLE for the carbon dioxide+1-hexanol system. However, in order to obtain good agreement with experimental data for the carbon dioxide+1-heptanol system, the mixture EoS parameters were adjusted to the experimental VLE data at each temperature.  相似文献   

6.
The mechanism and kinetics for the reaction of propene(CH3CH=CH2) molecule with O(1D) atom were investigated theoretically. The electronic structure information of the potential energy surface(PES) was obtained at the B3LYP/6-311+G(d,p) level, and the single-point energies were refined by the multi-level MCG3-MPWB method. The calculated results show that O(1D) atom can attack CH3CH=CH2 via the barrierless insertion mechanism to form four energy-riched intermediates CH3C(OH)CH2(IM1), CH3CHCHOH(IM2), CH2OHCHCH2(IM3) and cyclo- CH2OCHCH3(IM4), respectively, on the singlet PES. The branching ratios as well as the pressure- and temperaturedependence of various product channels for this multi-well reaction were predicted by variational transition-state and Rice-Ramsperger-Kassel-Marcus(RRKM) theories. The present results will be useful to gain a deep insight into the reaction mechanism and kinetics of CH3CH=CH2+O(1D) reaction.  相似文献   

7.
Compounds [n-CnH2n+1N(CH3)3]2CoCl4(n=16, C16C3Co; n=18, C18C3Co) containing lipid-like bilayers embedded in a crystalline matrix exist in solid-solid phase transition. The low-temperature bilayer structures of the two compounds were organized by neutralizing CoCl42- with alkylammonium ions. Alkyl chains lay parallel to each other and slightly tilted with respect to the normal of the inorganic layers. The adjacent alkyl chains interacted with each other by van der Waals interaction. When the temperature increased, the two compounds underwent a reversible solid-solid phase transformation within 310―330 K. In such a case, the chains showed a large motional freedom, and a disordered phase appeared. The structures can alternatively be viewed as a double layer of alkylammonium ions between CoCl42- sheets and be considered as crystalline models of lipid bilayers. The experimental subsolidus binary phase diagram of [n-C16H33N(CH3)3]2CoCl4-[n-C18H37N(CH3)3]2CoCl4 was constructed over the entire composition range by differential scanning calorimetry and X-ray diffraction technique. Experimental phase diagram indicates one stable intermediate phase [n-C16H33N(CH3)3][n-C18H37N(CH3)3]CoCl4 at wC16C3Co= 39.89% and two invariant three- phase equilibria, which shows two eutectoid temperatures: Te1 at (316±1) K for wC16C3Co= 27.35% and Te2 at (313±1) K for wC16C3Co=59.76%. These three noticeable solid-solution ranges are α-phase at the left, β-phase at the right, and γ-phase in the middle of the phase diagram.  相似文献   

8.
We have applied cavity ring-down spectroscopy to a kinetic study of the reaction of NO3 with CH2I2 in 25–100 Torr of N2 diluent at 298 K. The rate constant of reaction of NO3 + CH2I2 is determined to be (4.0 ± 1.2) × 10−13 cm3 molecule−1 s−1 in 100 Torr of N2 diluent at 298 K. The rate constant increases with increasing pressure of buffer gas below 100 Torr. The reaction of CH2I2 with NO3 has the potential importance at nighttime in the atmosphere.  相似文献   

9.
Two novel hydrogen maleato (HL) bridged Cu(II) complexes 1[Cu(phen)Cl(HL)2/2] 1 and 1[Cu(phen)(NO3)(HL)2/2] 2 were obtained from reactions of 1,10-phenanthroline, maleic acid with CuCl2·2H2O and Cu(NO3)2·3H2O, respectively, in CH3OH/H2O (1:1 v/v) at pH=2.0 and the crystal structures were determined by single crystal X-ray diffraction methods. Both complexes crystallize isostructurally in the monoclinic space group P21/n with cell dimensions: 1 a=8.639(2) Å, b=15.614(3) Å, c=11.326(2) Å, β=94.67(3)°, Z=4, Dcalc=1.720 g/cm3 and 2 a=8.544(1) Å, b=15.517(2) Å, c=12.160(1) Å, β=90.84(8)°, Z=4, Dcalc=1.734 g/cm3. In both complexes, the square pyramidally coordinated Cu atoms are bridged by hydrogen maleato ligands into 1D chains with the coordinating phen ligands parallel on one side. Interdigitation of the chelating phen ligands of two neighbouring chains via π–π stacking interactions forms supramolecular double chains, which are then arranged in the crystal structures according to pseudo 1D close packing patterns. Both complexes exhibit similar paramagnetic behavior obeying Curie–Weiss laws χm(T−θ)=0.414 cm3 mol−1 K with the Weiss constants θ=−1.45, −1.0 K for 1 and 2, respectively.  相似文献   

10.
The excess molar volumes VmE {x(CH3OH or CH3CH2OH or CH3(CH2)2OH or CH3CH(OH)CH3 + (1 - x){CH3(CH2)2}2O or CH3C(CH3)2OCH3 or CH3CH2C(CH3)2OCH3} have been calculated from measured values of density over the whole composition range at the temperature 298.15 K in order to investigate OH … O specific interactions. The results are explained in terms of the strong self-association of the alkanols, the specific interaction between the alkanol, and the ether molecules and packing effects upon mixing. The experimental Vmh results presented here, together with the previously reported data for the molar excess enthalpy HmE, has been used to test the Extended Real Associated Solution (ERAS) model.  相似文献   

11.
Variable temperature (−55 to −150°C) studies of the infrared spectra (3500–400 cm−1) of 1-chloropropane (CH3CH2CH2Cl) and 1-bromopropane (CH3CH2CH2Br) dissolved in liquid krypton and xenon, respectively, have been recorded. Utilizing two conformer pairs in krypton solution for chloride and three conformer pairs in xenon solution for bromide, enthalpy differences of 52±3 cm−1 (0.62±0.06 kJ/mol) and 72±7 cm−1 (0.86±0.08 kJ/mol) were obtained for the chloride and bromide, respectively, with the gauche form being the more stable conformer for both molecules. From these data, it is estimated that 28 and 26% of trans form are present at ambient temperature for the chloride and bromide, respectively. The conformation stabilities, harmonic force constants, fundamental frequencies, infrared intensities and Raman activities have been obtained from RHF/6-31G(d) and/or MP2/6-31G(d) ab initio calculations for both halopropanes and these quantities have been compared to the experimental values when appropriate. The optimized geometries have also been obtained with several different ab initio basis sets with full electron correlation by the perturbation method up to MP2/6-311+G(2d,2p). The r0 structural parameters of both halopropanes have been obtained by combining the ab initio data with the previously reported microwave rotational constants for both conformers. The quantities are compared to the corresponding results for some similar molecules.  相似文献   

12.
2-Methyl pyrazine (2MP) has led to significant interest for its industrial and pharmaceutical uses. The new vapor–liquid equilibria (VLE) at 353.15 K and excess molar volumes (VE) at 298.15 K over the whole mole fraction range for seven binaries (water, n-hexane, cyclohexane, n-heptane, methylcyclopentane (MCP), methylcyclohexane (MCH) and ethyl acetate (EA) with 2MP) have been measured. VLE were measured by using headspace gas chromatography and VE were determined using precision density meter. The water+2MP system has only the minimum boiling azeotrope. The experimental VLE and VE data were well correlated in terms of common gE models and Redlich–Kister equation, respectively.  相似文献   

13.
The infrared spectra of phosphinic acid R2POOH dimers (R=CH3, CH2Cl, C6H5) have been studied in CCl4 and CH2Cl2 solutions (T=300 K). The infrared spectra of deuterated R2POOD dimers (R=CH3, CH2Cl) were also studied in the gas phase (T=400–550 K) and solid state (T=100–300 K). They are compared with previously studied spectra of the light (non-deuterated) dimers in the gas phase, in the solid state and in low-temperature argon matrices (T=12–30 K) in the 4000–400 cm−1 spectral region. It is found that the strong and broad ν(OH) dimer bands have similar shapes, nearly equal values of bandwidth and low-frequency shift, and possess the Hadzi ABC structure irrespective of the type of acid, significant differences of dimerization enthalpies, influence of solvent, the type of H-bonded complexes (cyclic dimers in the gas phase, in solutions, and in inert matrices, and infinite chains in the solid state), and temperature in the range 12–600 K. Isotopic ratio of the first moments of light and deuterated acid bands has been measured. Analysis of the ν(OH/OD) band of hydrogen bonded dimers of phosphinic acids shows that the interaction between the two intermolecular bonds O–HOP in a cyclic complex plays virtually no role in the mechanism of the ν(OH/OD) band formation; the shape of ν(OH/OD) band is controlled mainly by the POOH(D)O fragment; and the band shape of strong hydrogen bonded complexes is formed by a number of vibrational transitions from the ground state to different combination levels in the region 3500–1500 cm−1.  相似文献   

14.
The infrared spectra of 3-pentyn-2-ol, CH3CCCH(OH)CH3, have been recorded as a vapour and liquid at ambient temperature, as a solid at 78 K in the 4000–50 cm−1 range and isolated in an argon matrix at ca. 5 K. Infrared spectra of the solid phase at 78 K were obtained before and after annealing to temperatures of 120 and 130 K. The IR spectra of the solid were quite similar to that of the liquid.

Raman spectra of the liquid were recorded at room temperature and at various temperatures between 295 and 153 K. Spectra of an amorphous and annealed solid were recorded at 78 K. In the variable temperature Raman spectra, some bands changed in relative intensity and were interpreted in terms of conformational equilibria between the three possible conformers. Complete assignments were made for all the bands of the most stable conformer in which OH is oriented anti to C1(aMe). From various bands assigned to a second conformer in which OH is oriented anti to Hgem(aH), the conformational enthalpy differences was found to be between 0.4 and 0.8 kJ mol−1. The highest energy conformer with OH anti to C3(aC) was not detected.

Quantum-chemical calculations have been carried out at the MP2 and B3LYP levels with a variety of basis sets. Except for small basis set calculations for which the aH conformer had slightly lower energy, all the calculations revealed that aMe was the low energy conformer. The B3LYP/cc-pVTZ calculations suggested the aMe conformer as more stable by 0.8 and 8.3 kJ mol−1 relative to aH an aC, respectively. Vibrational wavenumbers and infrared and Raman band intensities for two of the three conformers are reported from B3LYP/cc-pVTZ calculations.  相似文献   


15.
Treatment of (2-C5H4N)CH2 3N (TPA) with one equivalent of MCl2 in n-BuOH at elevated temperatures affords the six-coordinate complexes [(TPA)MCl2] (M = Co (1), Fe (2)) and, in the case of CoCl2, the five-coordinate chloride salt [(TPA)CoCl]Cl (3). Conversely, addition of an excess of CoCl2 in the latter reaction leads to [(TPA)CoCl]2[CoCl4] (4) as the only isolable product. Interaction of one equivalent of (2-C5H4N)CH2 2NH (DPA) and MCl2 under similar reaction conditions to that described above affords the dimeric species [(fac-DPA)MCl(μ-Cl)]2 (M = Co (5), Fe (6)), while the bis(ligand) halide salts [(fac-DPA)2M]Cl2 (M = Co (7), Fe (8)) are accessible on addition of two equivalents of DPA. In the presence of air, 6 undergoes oxidation to give [ (fac-DPA)FeCl2 2(μ-O)] (9). Single-crystal X-ray diffraction studies are reported for 1, 2 · MeCN, 3, , 7 · 3MeCN, 8 · 3MeCN and 9.  相似文献   

16.
Mechanisms of RN3 (R=CH3, CH3CH2, (CH3)2CH, (CH3)3C) dissociations are proposed based on CAS, MP2 and B3LYP methods. The energy gaps between the ground-state reactants RN3 and the intersystem crossing (ISC) points are only a little lower than respective potential energy barriers of the spin-allowed reactions, 1RN3 → 1RN + 1N2. The ISC point, therefore, is considered as a transition state of the spin-forbidden reactions, 1RN3 → 3RN + 1N2. The methods of IRC and topological analysis of electron density are used to explain and predict the thermal dissociation pathways of the reactions studied.  相似文献   

17.
The reaction of [(C6H6)RuCl2]2 with 7,8-benzoquinoline and 8-hydroxyquinoline in methanol were performed. The obtained complexes have been studied by IR, UV–VIS, 1H and 13C NMR spectroscopy and X-ray crystallography. In the reaction with 8-hydroxyquinoline the arene ruthenium(II) complex oxidized to Ru(III). The electronic spectra of the obtained compounds have been calculated using the TDDFT method. Magnetic properties of [Ru(C9H6NO)3] · CH3OH complex suggest the antiferromagnetic coupling of the ruthenium centers in the crystal lattice. EPR spectrum of [Ru(C9H6NO)3] · CH3OH compound indicates single isotropic line only characteristic for Ru3+ with spin equal to 1/2.  相似文献   

18.
Sn(CH3)2Cl2 exerts its antitumor activity in a specific way. Unlike anticancer cis-Pt(NH3)2Cl2 drug which binds strongly to the nitrogen atoms of DNA bases, Sn(CH3)2Cl2 shows no major affinity towards base binding. Thus, the mechanism of action by which tinorganometallic compounds exert antitumor activity would be different from that of the cisplatin drug. The aim of this study was to examine the binding of Sn(CH3)2Cl2 with calf thymus DNA and yeast RNA in aqueous solutions at pH 7.1–6.6 with constant concentrations of DNA and RNA and various molar ratios of Sn(CH3)2Cl2/DNA (phosphate) and Sn(CH3)2Cl2/RNA of 1/40, 1/20, 1/10, 1/5. Fourier transform infrared (FTIR) and UV–visible difference spectroscopic methods were used to determine the Sn(CH3)2Cl2 binding mode, binding constant, sequence selectivity and structural variations of Sn(CH3)2Cl2/DNA and Sn(CH3)2Cl2/RNA complexes in aqueous solution. Sn(CH3)2Cl2 hydrolyzes in water to give Sn(CH3)2(OH)2 and [Sn(CH3)2(OH)(H2O)n]+ species. Spectroscopic evidence showed that interaction occurred mainly through (CH3)2Sn(IV) hydroxide and polynucleotide backbone phosphate group with overall binding constant of K(Sn(CH3)2Cl2–DNA)=1.47×105 M−1 and K(Sn(CH3)2Cl2–RNA)=7.33×105 M−1. Sn(CH3)2Cl2 induced no biopolymer conformational changes with DNA remaining in the B-family structure and RNA in A-conformation upon drug complexation.  相似文献   

19.
Six new cluster derivatives [Rh2Co2(CO)6(μ-CO)442-HCCR)] (R=FeCp2 1, CH2OH 2, (CH3O)C10H6CH(CH3)COOCH2CCH 3) and [RhCo3(CO)6(μ-CO)442-HCCR)] (R=FeCp2 4, CH2OH 5, (CH3O)C10H6CH(CH3)COOCH2CCH 6) were obtained by the reactions of [Rh2Co2(CO)12] and [RhCo3(CO)12] with substituted 1-alkyne ligands HCCR [R=FeCp2 7, CH2OH 8, (CH3O)C10H6CH(CH3) COOCH2CCH 9] in n-hexane at room temperature, respectively. Alkynes insert into the Co---Co bond of the tetranuclear clusters to give butterfly clusters. [Rh2Co2(CO)6(μ-CO)442-HCCFeCp2)] (1) was characterized by a single-crystal X-ray diffraction analysis. Reactions of 1, 2 with 7, 8 and ambient pressure of carbon monoxide at 25 °C gave two known cluster complexes [Co2(CO)62, η2-HCCR)] (R=FeCp2 10, CH2OH 11), respectively. All clusters were characterized by element analysis, IR and 1H-NMR spectroscopy.  相似文献   

20.
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl2(P-P)] (P-P = (PPh3)2, Ph2P(CH2)3PPh2, Phd2P(CH2)4PPh2; 1,4-dithiols = HS(CH2)4SH, (−)DIOSH2 (2,3-O-isopropylidene-1,4-dithiol-l-threitol), BINASH2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph2P(CH2)3PPh2, Ph2P(CH2)4PPh2; dithiolato = S(CH2)4S, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh3)2] and [Pd(S(CH2)4S)(Ph2P(CH2)3PPh2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC12 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%.  相似文献   

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