A DFT study of R-R reductive elimination (R = Me, Ph, vinyl) in plausible intermediates of Pd-catalyzed processes is reported. These include the square-planar tetracoordinated systems cis-[PdR(2)(PMe(3))(2)] themselves, possible intermediates cis-[PdR(2)(PMe(3))L] formed in solution or upon addition of coupling promoters (L = acetonitrile, ethylene, maleic anhydride (ma)), and tricoordinated intermediates cis-[PdR(2)(PMe(3))] (represented as L = empty). The activation energy ranges from 0.6 to 28.6 kcal/mol in the gas phase, increasing in the order vinyl-vinyl < Ph-Ph < Me-Me, depending on R, and ma < "empty" < ethylene < PMe(3) approximately MeCN, depending on L. The effect of added olefins was studied for a series of olefins, providing the following order of activation energy: p-benzoquinone < ma < trans-1,2-dicyanoethylene < 3,5-dimethylcyclopent-1-ene < 2,5-dihydrofuran < ethylene < trans-2-butene. Comparison of the calculated energies with experimental data for the coupling of cis-[PdMe(2)(PPh(3))(2)] in the presence of additives (PPh(3), p-benzoquinone, ma, trans-1,2-dicyanoethylene, 2,5-dihydrofuran, and 1-hexene) reveals that: (1) There is no universal coupling mechanism. (2) The coupling mechanism calculated for cis-[PdMe(2)(PMe(3))(2)] is direct, but PPh(3) retards the coupling for cis-[PdMe(2)(PPh(3))(2)], and DFT calculations support a switch of the coupling mechanism to dissociative for PPh(3). (3) Additives that would provide intermediates with coupling activation energies higher than a dissociative mechanism (e.g., common olefins) produce no effect on coupling. (4) Olefins with electron-withdrawing substituents facilitate the coupling through cis-[PdMe(2)(PR(3))(olefin)] intermediates with much lower activation energies than the starting complex or a tricoordinated intermediate. Practical consequences are discussed.

Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results.

Conductivities and dielectric constant measurements in water at 25 °C have been made on the amphiphilics sodium n-dodecyl sulfate, n-dodecyltrimethylammonium bromide, and chlorpromazine hydrochloride. By using the conductivity/concentration data, critical micelle concentrations (cmc) have been determined by applying the Williams definition and two forms of the Phillips method. This first Phillips form consists of an approximation to Gaussians of the second derivative of the conductivity/concentration data followed by two consecutive integrations. The second form, which is proposed here, consists of the application of a combination of the Runge-Kutta numerical integrations method and the Levenberg-Marquardt leastsquares fitting algorithm. The proposed method permits the determination of the cmc in systems with low aggregation numbers and with slow variations of physical property/concentration curves allowing the determination of the so-called second cmc. A comparative study with results obtained by dielectric constant measurements has been carried out. With this new technique, the cmc's (first and second) are directly obtained as singular points in the dielectric constant/concentration curves, and thus, this technique is an alternative to the determination of cmc's from conductivities.

We performed molecular dynamics simulations of mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate with lithium tetrafluoroborate and potassium tetrafluoroborate between two charged and uncharged graphene walls, in order to analyze the structure of the well-known formation of layers that takes place on liquids under confinement. For this purpose, we studied the molecular density profiles, free energy profiles for bringing lithium and potassium cations from the bulk mixture to the graphene wall and the orientational distributions of imidazolium rings within the first adsorbed layer as a function of salt concentration and electrode potential. The charge densities in the electrodes were chosen to be zero and ±1 e nm(-2), and the salt molar percentages were %salt = 0, 10 and 25. We found that the layered structure extends up to 1-2 nm, where the bulk behaviour is recovered. In addition, whereas for the neutral surface the layers are composed of both ionic species, increasing the electrode potential, the structure changes to alternating cationic and anionic layers leading to an overcompensation of the charge of the previous layer. We also calculated the distribution of angles of imidazolium rings near neutral and charged graphene walls, finding a limited influence of the added salt. In addition, the average tilt of the imidazolium ring within the first layer goes from 36° with respect to a normal vector to the uncharged graphene wall to 62° in the presence of charged walls. The free energy profiles revealed that lithium and potassium ions are adsorbed on the negative surface only for the highest amount of salt, since the free energy barriers for approaching this electrode are considerably higher than kBT.

The effect of some selected ligands (L = empty, PMe3, ethylene, maleic anhydride) in the reductive elimination of the palladium complexes cis-[Pd(η1-allyl)(η1-allyl)(PMe3)L] and Pd(η1-allyl)(η3-allyl)L to form hexa-1,5-diene was computationally studied using DFT methods. Among the various possible coupling processes (C1sp3 −C1′sp3 , C3sp2 −C3′sp2 , and C1sp3 −C3′sp2 ), C3−C3′ bond formation is the most favored in all cases, as reported before for cis-[Pd(η1-allyl)(η1-allyl)(PH3)2]. Interestingly, the activation energy for this coupling changes with the L ligand: empty (4.6 kcal/mol) < MA (5.8 kcal/mol) < CH2CH2 (12.5 kcal/mol) < PMe3 (17.3 kcal/mol). Therefore, tricoordinated Pd(η1-allyl)(η1-allyl)L complexes undergo reductive elimination at higher rates than the tetracoordinated counterparts. The order L = empty < L = MA is inverse to that found for carbon ligands (alkyl, aryl, alkenyl) that couple via direct C1−C1′ reductive elimination; the order L = empty < L = MA is also followed by the allyl groups when the disfavored C1−C1′ bond formation is considered. Structural analysis reveals that the C3−C3′ reductive elimination of cis-[Pd(η1-allyl)2(PMe3)] is particularly favored by the small distortion of the original T-shaped geometry in the transition state, which preserves the hyperconjugative dσ(C1−Pd)→π*(C2C3)-type interaction between the metal and the allyl substituents. The activation energies for the elimination of allyl groups are intermediate between those of alkenes/arenes and alkyls when palladium complexes with similar composition cis-[Pd(R)(R)(PMe3)L] are compared. Although the effect is more moderate than in other carbon substituents, π-acceptor ligands (MA) and to a lesser extent olefins (exogenous or the same substrates/products) are efficient additives in this coupling, an electronic effect that is conveyed to the distant C3 and C3′ atoms by the entire interacting system. Consistent with this proposal, the transition state for the C3sp2 −C3′sp2 reductive elimination in cis-[Pd(η1-allyl)(η1-allyl)(PMe3)L] shares both structural and electronic features with a pericyclic (homo)Cope rearrangement.

CO2 and CH4 clathrate hydrates of type I were studied by means of DFT and QTAIM, in order to better understand their properties at the molecular level. Sub-cells of type I hydrates were modeled as independent rigid cages, both empty and containing guest molecules. Interaction potentials of guest molecules inside each cage, and moving from a cell to the adjacent one, were calculated using the DFT approximation B3LYP/6-311+g(d,p), considering the cases with and without long range Coulombic corrections. The selected theory level was validated by comparison of the simulated Raman spectra with the experimental ones, for the case of type I lattice at full occupation of CO2 and CH4, respectively. For this comparison, Fermi resonances of CO2 were taken into account by transforming experimental bands to the corresponding theoretical non-mixed states. On the one hand, our results confirm the validity of the theory level selected for the model. We have shown the high anisotropy of the guest-cell interaction potential of the molecules analyzed, which has implications in the formulation and use of equations of state, and in the study of transport properties as well. On the other hand, our results suggest that the concentration of guest species inside type I hydrates could be computed from the comparison of experimental and predicted Raman spectra, although there are non-trivial experimental limitations to get over for that purpose.

In this work, we use dual cage explicit atomic systems to demonstrate theoretically that direct transitions are feasible through hexagonal and pentagonal faces in type I hydrate without compromising the overall structure integrity.

The rheological behavior of ethylene glycol-based nanofluids containing exfoliated graphite nanoplatelets has been carried out using a cone-plate Physica MCR rheometer. Initial experiments based on flow curves were carried out, the flow curves were based on the controlled shear stress model, these tests show that the studied nanofluids present non-Newtonian shear thinning behavior with yield stress. Furthermore, linear viscoelastic experiments were conducted in order to determine the viscoelastic behavior: using strain sweep and frequency sweep tests the storage and loss modulus were determined. The fractal dimension (Df) was estimated from the suspension static yield-stress and volume fraction (ϕ) dependence, and was determined to be Df = 2.36, a value consistent with a process of aggregation of RLCA type (reaction limited cluster aggregation). This value is unusual if compared with other nanofluids, and can be regarded as a result of the bidimensionality of the suspended nanoplatelets. Finally, creep-recovery tests and mechanical models confirm the viscoplastic nature of our nanofluids, a feature never shown so far for this type of systems, increasing the solid-like character in the range of concentrations studied if compared with other nanofluids reported in the literature. This is a result of the combination of a remarkable internal structure and strong interactions, which evidence an unexpected behaviour sharing many solid-like features.