Volumetric,acoustic, and viscometric studies of molecular interactions in binary mixtures of diethylene glycol monomethyl ether with 1-alkanols at temperatures from (293.15 to 308.15) K

In this work, densities ρ, speeds of sound u, and viscosities η, have been measured over the whole composition range for the binary mixtures of diethylene glycol monomethyl ether (DEGMME), CH₃(OCH₂CH₂)₂OH with 1-hexanol, CH₃(CH₂)₅OH, 1-octanol, CH₃(CH₂)₇OH, and 1-decanol, CH₃(CH₂)₉OH at T = (293.15, 298.15, 303.15, and 308.15) K along with the properties of the pure components. By using the experimental values of ρ, u, and η, excess molar volume, $V_m^E$, deviations in viscosity, Δη, isentropic compressibility κ_S, deviations in isentropic compressibility Δκ_S, deviations of the speed of sound Δu, have been calculated. The viscosity results have also been analysed in terms of some semi-empirical equations.     

Ultrasonic speeds and thermodynamic properties of (benzene + nitrobenzene) under high pressures

Ultrasonic speeds u in {(1?x)C₆H₆ + xC₆H₅NO₂} were measured by a fixed-path pulse technique at 293.15, 303.15, and 313.15 K under pressures up to 30 or 200 MPa with an observed error of less than 0.3 per cent. Curves of u(x) change smoothly in the benzene-rich region. But near x = 0.7, u(x) apparently deviates from a smooth curve, and the apparent gap becomes progressively greater as the temperature is reduced or the pressure is raised. From the experimental values, densities, isentropic compressibilities, and expansivities were calculated at high pressures. These quantities also show unusual behavior with x similar to that of u.     

Densities,speeds of sound and isentropic compressibilities of binary and ternary mixtures containing benzene,cyclohexane and hexane at 298.15 K

Densities, ϱ, and speeds of sound, u, have been measured for the ternary mixture {benzene + cyclohexane + hexane} and the corresponding binary mixtures {benzene + cyclohexane}, {benzene + hexane} and {cyclohexane + hexane}, at the temperature 298.15 K. Using these results, the isentropic compressibilities, κ_s, the excess isentropic compressibilities, κ_s^E, and the speeds of sound deviations, Δu, have been calculated for both the binary mixtures and the ternary system. Excess isentropic compressibilities, κ_s^E, and the speeds of sound deviations, Δu, have been fitted to the Redlich-Kister equation in the case of binary mixtures, while the equation of Cibulka was used to fit the values relating to the ternary system. The empiric equations of Redlich-Kister, Tsao-Smith, Kohler and Colinet have been applied in order to predict the κ_s^E and Δu of ternary mixtures from the binary contributions.     

Speeds of sound and isentropic compressibilities of binary mixtures containing trialkylamines with alkanes and mono-alkylamines at 303.15 and 313.15 K

Isentropic compressibilities κ_S, and excess isentropic compressibilities κ_S^E have been determined from measurements of speeds of sound u and densities ρ of 14 binary mixtures of triethylamine (TEA) and tri-n-butylamine (TBA) with n-hexane, n-octane, iso-octane, n-propylamine, n-butylamine, n-hexylamine and n-octylamine. The relative magnitude and sign of κ_S^E have been interpreted in terms of molecular interactions and interstitial accommodation. The values of κ_S^E for TEA + alkane are positive while for TBA + alkane are negative. The values of κ_S^E for TEA + primary amine become progressively less positive and eventually to negative with the increase in chain length of alkylamine. In case of TBA + primary amine, the values of κ_S^E increase from n-propylamine to n-butylamine, and then decrease with chain length of primary amine. The experimental speeds of sound u have been analyzed in terms of collision factor theory, free length theory and Prigogine–Flory–Patterson statistical theory of solutions.     

Coordination chemistry of an asymmetric P,N,O tridentate ligand containing primary phosphine, amine and alcohol donors

The asymmetric, heterodonor tridentate ligand 2(S)-amino-4-phosphinobutan-1-ol, S-PNO, has been prepared from (S)-aspartic acid and some aspects of its coordination chemistry with a number of metal complexes investigated. Reaction of S-PNO with appropriate metal precursors led to the isolation of the complexes fac-Cr(CO)₃(κ³-S-PNO), 1, fac-[Mn(CO)₃(κ³-S-PNO)]PF₆, 2, and fac-[Re(CO)₃(κ³-S-PNO)]BF₄, 3. The alcohol and amine donors in fac-Cr(CO)₃(κ³-S-PNO) were substituted upon addition of trivinylphosphine to 1 to give the complex fac-Cr(CO)₃(κ¹-P-S-PNO){P(C₂H₃)₃}₂, 4. Addition of base to 4 gave a coordinated linear tridentate P₃ ligand through the formation of two new chelate rings via hydrophosphination of one vinyl group on each coordinated P(C₂H₃)₃ with the P-H bonds of the complexed S-PNO. The alcohol donor in fac-[Re(CO)₃(κ³-S-PNO)]BF₄ is labile and can be substituted with tris(2-fluorophenyl)phosphine, PAr₃^F, to give fac-[Re(CO)₃(κ²-P,N-S-PNO)(PAr₃^F)]BF₄, 5. Attempts to form a macrocyclic ligand through addition of base to fac-[Re(CO)₃(κ²-P,N-S-PNO)(PAr₃^F)]BF₄ were unsuccessful due to loss of PAr₃^F prior to any ring-closure. All the complexes have been fully characterised by spectroscopic and analytical techniques including a single-crystal X-ray structure analysis of 2.     

Large-scale configuration interaction calculations on the π-electron states of benzene

Ab initio extensive configuration interaction calculations were carried out on the π-electron states of benzene. Among the three π → π^*(e_1g → e_2u) singlet states, ¹B_2u(S₁). ¹B_1u(S₂), and ¹E_1u(S₃), the π^* orbital was found to be velence-like in S₁ and S₂, but diffuse in S₃. All three corresponding triplet states, ³B_1u(T₁) and ³B_2u(T₃), were found to be valence-like. The valence-like ¹E_2g(S₄) and ³E_2g(T₄) states were found to have significant double-excitation character, and were estimated to lie somewhat above S₃ and T₃, respectively. No low-lying S₅ and T₅ states were found. Several low-lying Rydberg states were identified.     

Speeds of sound and isentropic compressibilities of (n-alkoxyethanols + toluene) at T = 298.15 K

Speeds of sound u at the temperature 298.15 K for six ( n -alkoxyethanol  +  toluene) were measured over the whole composition range. The n -alkoxyethanols were 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, and 2-(2-butoxyethoxy)ethanol. Excess molar volumes V_m^E atT =  298.15 K were also measured for the mixtures of toluene and 2-methoxyethanol, 2-ethoxyethanol, or 2-butoxyethanol over the whole composition range. The speed of sound values were combined with excess molar volumes to obtain values for the product K_{S, m} of the molar volume and the isentropic compressibilityκ_S , and the corresponding excess quantities K_S,m^E were also calculated. The K_S,m^E curves are sigmoid for all mixtures. The deviations of the speeds of soundu^D from their values u^id in an ideal mixture were obtained for all measured mole fractions. These values are compared with the mixing function δu calculated in the paper. The behaviour ofu , u^D, δu, and K_S,m^E as a function of composition and number of carbon atoms in the aliphatic chain of the alkoxyethanol is discussed. Also, theoretical values of the molar isentropic compressibility K_S,m and speed of sound u were calculated using the Prigogine-Flory-Patterson theory with a van der Waals potential energy model and the results compared with experimental data.     

Synthesis and properties of alkylruthenium complexes bearing primary and secondary amine ligands

A series of 18-electron alkylruthenium complexes, RuR[κ²(N,N′)-(S,S)-R′SO₂NCHPhCHPhNH₂](η⁶-arene) (Ph = C₆H₅, R′ = p-CH₃C₆H₄ and CH₃), bearing a N-sulfonylated diamine ligand was synthesized from the reaction of RuCl[κ²(N, N′)-(S,S)-R′SO₂NCHPhCHPhNH₂](η⁶-arene) with alkylzinc reagents, in which transmetalation proceeded smoothly to give the desired alkyl complexes in good yield and selectivity. Although the isolable amine Ru complexes bearing functionalized alkyl ligands were thermally stable, the simple methyl and ethyl Ru complexes underwent intramolecular deprotonation from NH protons to give the amido Ru complexes with release of the alkanes. The reactivity of the alkyl Ru complexes is highly affected by the structures of the arene ligands.     

Synthesis and structure of new palladium complexes with the ligand 2-(diphenylphosphino)-1-methylimidazole: Evidence of hemilability

Several Pd(II) complexes containing the potentially bidentate ligand 2-(diphenylphosphino)-1-methylimidazole, dpim, have been synthesized and characterized: [PdCl₂(dpim)]_n (1), [PdCl₂(H₂O)(dpim-κP)] (2), [PdClMe(μ-dpim-κP,κN)]₂ (3) (previously described), [PdClMe(dpim-κP)₂] (4), [Pd(C₆F₅)₂(dpim-κP)₂] (5) and [Pd(η³-2-Me-C₃H₄)(μ-dpim-κP,κN)]₂[PF₆]₂ (6). The highly insoluble complex 1 dissolves in wet DMSO-d₆ to give the water adduct 2 in which a hydrogen bond is established between one of the water hydrogens and the imidazolyl nitrogen. Two types of coordination mode have been found for the dpim ligand in these derivatives, with the ligand behaving as P monodentate and also as a P,N bridge. The transformations between 3 and 4 demonstrate the hemilability of the dpim ligand. Complex 6 was obtained as a mixture of two pairs of enantiomers (R,S)/(S,R) and (R,R)/(S,S). Analysis of the fluxional behaviour of 6, in which the allyl group acts as a “reporter ligand”, indicates that Pd-N bond rupture takes place - again providing evidence of the hemilabile character of the dpim ligand.     

A new method to calculate the thermodynamical properties of liquids from accurate speed-of-sound measurements

In this work, a new method for the determination of the thermodynamical properties of fluids, based on experimental speed-of-sound measurements, is described. This method consists in the solution of recursive equations (REM, Recursive Equations Method) for the determination of the density ρ(p,T) and specific heat capacity at constant pressure c_p(p,T), using the initial values of density ρ(p₀,T) and isobaric specific heat capacity c_p(p₀,T) known at a reference pressure p₀, as a function of the temperature, if the speed-of-sound function, u(p,T), is known, at least over a certain temperature and pressure range. A complete uncertainty analysis has also been developed. As an example of the good performances of this analysis method, firstly density and isobaric specific heat capacity have been calculated for water and the results have been compared with those predicted by the International Association for the Properties of Water and Steam 95 Formulation (IAPWS-95), as delivered by Wagner and Pruss. One more application has been made starting from experimental speed-of-sound values in pure acetone. These results have been compared with those calculated by the most advanced numerical integration methods and with the prevision of the dedicated NIST equation of state (EoS) by Lemmon and Span.     

Ruthenium complexes that incorporate a chiro-inositol derived diphosphinite ligand as catalysts for asymmetric hydrogenation reactions

The diol, 1d-1,2,5,6-tetra-O-methyl-chiro-inositol (D-9), can be conveniently prepared from 1d-chiro-inositol using a series of standard protection/deprotection steps. Treatment of D-9 with Ph₂PCl gives the chiral diphosphinite, 1d-3,4-bis(O-diphenylphosphino)-1,2,5,6-tetra-O-methyl-chiro-inositol (D-10). The structure of D-10 has been determined by X-ray crystallography. Using 1l-chiro-inositol as starting material and following the same synthetic sequence used to produce D-10, the other enantiomer of this diphosphinite, 1l-3,4-bis(O-diphenylphosphino)-1,2,5,6-tetra-O-methyl-chiro-inositol (L-10) can also be obtained. Ruthenium complexes of these diphosphinite ligands can be conveniently prepared through ligand substitution reactions with appropriate substrate complexes. Thus, treatment of [RuCl₂(COD)]_n with D-10 in the presence of triethylamine produces the bis(diphosphinite) complex, RuHCl{κ²(P,P)-1d-3,4-bis(O-diphenylphosphino)-1,2,5,6-tetra-O-methyl-chiro-inositol}₂ (11). In addition, reaction between RuCl₂(PPh₃)₃, D-10 and (1R,2R)-(+)-1,2-diphenylethylenediamine gives the mono(diphosphinite) complex, RuCl₂{κ²(P,P)-1d-3,4-bis(O-diphenylphosphino)-1,2,5,6-tetra-O-methyl-chiro-inositol}{κ²(N,N)-(1R,2R)-(+)-1,2-diphenylethylenediamine} (12). The closely related complex RuCl₂{κ²(P,P)-1d-3,4-bis(O-diphenylphosphino)-1,2,5,6-tetra-O-methyl-chiro-inositol}{κ²(N,N)-(1S,2S)-(−)-1,2-diphenylethylenediamine} (13) can be obtained in a similar manner using (1S,2S)-(−)-1,2-diphenylethylenediamine in place of the corresponding (+)-isomer. These new chiral, diphosphinite complexes catalyse the hydrogenation of the ketones acetophenone and 3-quinuclidinone to give the corresponding alcohols with low to moderate enantiomeric excesses. The complexes are not catalytically active for the hydrogenation of the olefin dimethylitaconate or the α-ketoester methyl benzoylformate.     

Volumetric and Acoustic Studies of Binary Liquid Mixtures of Dipropylene Glycol Dimethyl Ether with Methyl Acetate, Ethyl Acetate and n-Butyl Acetate in the Temperature Range T = (288.15, 293.15, 298.15, 303.15, and 308.15) K

Densities and ultrasonic speeds have been measured over the whole composition range for binary liquid mixtures of dipropylene glycol dimethyl ether, CH₃(OC₃H₆)₂OCH₃, with methyl acetate, ethyl acetate, and n-butyl acetate using an Anton Paar DSA 5000 M density and speed sound analyzer at T = (288.15, 293.15, 298.15, 303.15, and 308.15) K and atmospheric pressure in order to evaluate the behavior of these binaries. From these data excess the molar volume, $ V_{m}^{\text{E}} $ , and deviation in isentropic compressibility, ?κ _S , have been calculated. These excess properties have been fitted with the Redlich–Kister type polynomial equation to get their coefficients and standard deviations which provide a base for discussing the forces operating in solutions.     

Synthesis and characterization of platinum and palladium pyrrolidinedithiocarbamate complexes

Treatment of (PPh₃)₂MCl₂ (M = Pd or Pt) with ammonium pyrrolidinedithiocarbamate (NH₄S₂CNC₄H₈) in a 1:1 molar ratio gave (PPh₃)M(Cl)(κ ² S,S-S₂CNC₄H₈) [M = Pt (1), Pd (2)]. On the other hand, the interaction of these compounds in a 1:2 [M:L] molar ratio gave (PPh₃)Pt(κS-S₂CNC₄H₈)(κ ² S,S-S₂CNC₄H₈) (3), which contains both terminal and chelated dithiocarbamato ligands, or a yellow insoluble solid for M = Pd. The bis(diphenylphosphino)ethane platinum or palladium dichlorides [(dppe)MCl₂] reacted with the same ligand to give the salts [(dppe)M(κ ² S,S-S₂CNC₄H₈)]Cl (M = Pt (4), Pd (5) which have only one chelating dithiocarbamato ligand. The new compounds were characterized by ¹H-, ¹³C{¹H}- and ³¹P-n.m.r. spectroscopy, mass spectrometry, elemental analysis and X-ray single crystal structure analysis.     

Some comments on vibronic intensities of naphthalene fluorescence spectra from single vibronic levels

It is shown that some features of intensity distribution among certain vibronic transitions in naphthalene molecule can be understood, when one takes into account adiabatic and nonadiabatic interaction between S₁(¹B_3u), S₂(^tB_2u), and S₃(^IB_3u) electronic states. the vibronic activity of the $\text{6}\text{?}$(b_1g) mode in naphthalene-d₈ can be explained in terms of an anharmonic coupling with the $\text{7}\text{?}$(b_1g) mode. The theoretical analysis suggests reinterpretation of some vibronic transitions.     

Burning velocity measurements of fluoropropanes by the spherical-vessel method

Burning velocity measurements of six types of fluoropropanes including structural isomers were carried out in order to understand the flammability of hydrofluorocarbons (HFC). The burning velocity (S_u) was determined by applying a spherical flame model to the pressure rise during combustion, which was measured at room temperature and at initial pressures of 80-107 kPa over a wide range of HFC/air concentrations. The maximum S_u of 1-fluoropropane (HFC-281fa), 2-fluoropropane (HFC-281ea), 1,3-difluoropropane (HFC-272fa), 2,2-difluoropropane (HFC-272ca), 1,2,3-trifluoropropane (HFC-263ea), and 1,1,1-trifluoropropane (HFC-263fb) was 35.0, 31.8, 31.9, 21.2, 25.7, and 14.5 cm s⁻¹, respectively. Note that the maximum S_u of HFC-263ea was appreciably higher than that of HFC-272ca, which shows the importance of the F-atom distribution, as well as of the F/H ratio in the HFC molecule. The results of equilibrium calculation for these HFCs showed that S_u is positively correlated with the flame temperature and the concentrations of the active chain carriers H and OH in the flame. We conducted a trial to interpret the magnitude of S_u by means of the effects of substituents for C₁-C₃ HFCs. As a result, it has been found that the order of inhibition efficiency for S_u decreases in the order of CF₃ > CF₂ > CF.     

Study of densities,viscosities, and speeds of sound of binary liquid mixtures of butan-1-ol with n-alkanes (C6, C8, and C10) at T = (298.15, 303.15, and 308.15) K

The densities (ρ) and speeds of sound (u) have been measured over the whole composition range for (butan-1-ol with hexane, or octane, or decane) at T = (298.15, 303.15, and 308.15) K and atmospheric pressure along with the properties of the pure components. Viscosities (η) of these binary mixtures have also been measured over the entire composition range at T = 298.15 K. Experimental values of density, viscosity and speed of sound have been used to evaluate excess properties viz. excess molar volumes (V^E), deviation in viscosity (Δη), deviation in speeds of sound (Δu), deviation in isentropic compressibility (Δκ_s) and excess Gibbs free energy of activation of viscous flow (ΔG^1E). The excess properties have been correlated using the Redlich–Kister polynomial equation. The sign and magnitude of these excess properties have been used to interpret the results in terms of intermolecular interactions and structural effects. The viscosity data have also been correlated by Grunberg and Nissan, Tamura–Kurata, and Hind correlation equations.     

Thermodynamic investigation of methyl salicylate/1-pentanol binary system in the temperature range from 278.15 K to 303.15 K

Densities (ρ), speeds of sound (u), isentropic compressibilities (k_s), refractive indices (n_D), and surface tensions (σ) of binary mixtures of methyl salicylate (MSL) with 1-pentanol (PEN) have been measured over the entire composition range at the temperatures of 278.15 K, 288.15 K, and 303.15 K. The excess molar volumes (V^E), excess surface tensions (σ^E), deviations in speed of sound (Δu), deviations in isentropic compressibility (Δk_s), and deviations in molar refraction (ΔR) have been calculated. The excess thermodynamic properties V^E, σ^E, Δu, Δk_s, and ΔR were fitted to the Redlich–Kister polynomial equation and the A_k coefficients as well as the standard deviations (d) between the calculated and experimental values have been derived. The surface tension (σ) values have been further used for the calculation of the surface entropy (S^S) and the surface enthalpy (H^S) per unit surface area. The lyophobicity (β) and the surface mole fraction $(x_2^{\text{S}})$ of the surfactant component PEN have been also derived using the extended Langmuir model. The results provide information on the molecular interactions between the unlike molecules that take place at the surface and the bulk.     

Etude de l'isomerisation du methyl-4 pentene-1 par l'hydrido diazote tris(triphenylphosphine)cobalt(I): CoHN2(PPh3)3

At 25°C, and under 1 to 7 bar nitrogen pressure, the isomerization of 4-methyl-1-pentene catalyzed in benzene by CoHN₂(PPh₃)₃ involves two active species: HCoN₂(S₁)(PPh₃)₂ and HCo(S₁)(PPh₃)₃, respectively, in greater quantities at higher (P(N₂) > 7 bars) and small quantities at P(N₂)  0 nitrogen pressures.The kinetic study shows that the rate of the reaction is always ruled by the equation:

     

Asymmetric transfer hydrogenation of ketones catalyzed by ruthenium(II) complexes bearing a chiral phosphinoferrocenyloxazoline ligand

The catalytic activity in asymmetric transfer hydrogenation of ketones using octahedral and half-sandwich (η⁵-indenyl and η⁶-arene) ruthenium(II) complexes containing the chiral ligand (4S)-2-[(S_p)-2-(diphenylphosphino)ferrocenyl]-4-(isopropyl)oxazoline (FcPN) has been explored. Catalytic studies with complex fac-[RuCl₂{η²(P,N)-FcPN}(PMe₃)₂] (1) show excellent TOF values (9600 h⁻¹). Experiments in the presence of free FcPN, which lead to an increase in conversion rates and ee values when the catalyst is complex [Ru(η⁵-C₉H₇){κ²(P,N)-FcPN}(PPh₃)][PF₆] (4) have been carried out. The characterization of the new complexes mer-trans-[RuCl₂{P(OMe)₃}₂{κ²(P,N)-FcPN}] and of the water-soluble complexes fac- and mer-trans-[RuCl₂(PTA)₂{κ²(P,N)-FcPN}] is also reported.     

Thermodynamic Properties of Aqueous Electrolyte Solutions. Compressibility Studies in 0.1, 0.5 and 1.0 mol⋅kg−1 Lithium Chloride Solutions at Temperatures from 278.15 to 323.15 K

Sound velocities in aqueous 0.1, 0.5 and 1.0 mol?kg^?1 lithium chloride solutions were determined at 1 K temperature intervals from 278.15 to 323.15 K. These velocities served to evaluate the isentropic compressibilities κ _S , the isothermal compressibilities κ _T , the apparent molar compressibilities K _2,φ , the isochoric thermal pressure coefficients (? P/? T) _V , the change of cubic expansion coefficients with pressure at constant temperature (? α/? P) _T , and the changes of heat capacities C _V with volume (? C _V /? V) _T and C _P with pressure (? C _P /? P) _T .