Search results for "SOLVENT"
showing 10 items of 1395 documents
Impact of the ΔPhe configuration on the Boc-Gly-ΔPhe-NHMe conformation: experiment and theory
2019
Conformational propensities of N-t-butoxycarbonyl-glycine-(E/Z)-dehydrophenylalanine N′-methylamides (Boc-Gly-(E/Z)-ΔPhe-NHMe) in chloroform were investigated by NMR and IR techniques. The low-temperature crystal structure of the E isomer was determined by single crystal X-ray diffraction and the experimental data were elaborated by theoretical calculations using DFT (B3LYP, M06-2X) and MP2 approaches. The β-turn tendencies for both isomers were determined in the gas phase and in the presence of solvent. The obtained results reveal that the configuration of ΔPhe residue significantly affects the conformations of the studied dehydropeptides. The tendency to adopt β-turn conformations is sign…
First donor stabilized-phosphenium copper(I) complexes
2012
Abstract The preliminary studies of coordination properties of one donor stabilized-phosphenium adduct have been explored in copper chemistry. The preparation as well as the characterization of first examples of donor stabilized-phosphenium copper(I) complexes is reported in the paper. Thus, the direct addition of CuBr.SMe2 to an equivalent amount of cationic P‐ligands (L1+ or L2+)(PF6), with and , following by a crystallization in acetonitrile/Et2O led to first copper complexes [(L1,2+)CuBr2−] 1 and 3 and [(L1,2+)Cu+(NCMe)3+](PF6−)2 2 and 4 in a 1:1 ratio. However, when DMF/Et2O mixture was used as crystallization solvent, a stable bromo-bridged copper(I) dimer 5 [(L2+)CuBr(DMF)]2 was obta…
Reactions of pyridine-2-carbaldimines with chloro-bridged palladium(II) and platinum(II) 2-methylallyl dimers. Solution behaviour of the cationic com…
1987
Abstract The reactions of pyridine-2-carbaldimines, py-2- CHNR (R = C6H4OMe-p, Me), with allylic dimers [MCl(n3-2-MeC3H4)]2 give rise to stoichiometry, concentration, solvent and temperature dependent equilibria, in which the cationic complexes [M(n3- 2-MeC3H4)(py-2-CHNR)]+ and the anion [MCl2(n3- 2-MeC3H4)]- or Cl- are involved. In general, the ligand/dimer reaction (1/1 molar ratio) yields the ionic products [M(n3-2-MeC3H4)(py-2-CHNR)]- [MCl2(n3-2-MeC3H4)], which can be isolated as solids, whereas the same reaction in a 1/0.5 molar ratio yields the species [M(n3-2-MeC3H4 )(py-2-CH NR)] Cl, which can be studied only in solution, but are easily converted into [M(n3-2-MeC3H4)(py-2-CH NR…
Control over the oxidative reactivity of metalloporphyrins. Efficient electrosynthesis of meso,meso-linked zinc porphyrin dimer.
2011
The electrochemical oxidation of zinc(II) 5,15-p-ditolyl-10-phenylporphyrin at its first oxidation potential leads to the formation of the corresponding meso-meso porphyrin dimer as the main product. The number of electrons abstracted, the addition of the hindered base 2,6-lutidine as well as operating in DMF, instead of a CH(2)Cl(2)/CH(3)CN mixture are the key parameters to obtain high yields of the desired coupling product. Indeed, when the electrolyses are carried out in the CH(2)Cl(2)/CH(3)CN mixture, the unexpected zinc(II) 5-chloro-10,20-p-ditolyl-15-phenyl porphyrin is produced as a by-product, the chlorine atom originating from the CH(2)Cl(2) solvent. The monomer and the dimer are c…
A remarkable rearrangement during reaction between triazolopyridinium ylides and dimethyl acetylenedicarboxylate
1991
Abstract The ylides from 2-acylmethyltriazolopyridinium salts ( 1 ) react with dimethyl acetylenedicarboxylate in toluene solution to give the 7-pyrroleninylpyrazolo[1,5-a]pyridines ( 5 ).
Toward an Understanding of the Molecular Mechanism of the Reaction between 1-Methylpyrrole and Dimethyl Acetylenedicarboxylate. An ab Initio Study
1998
The molecular mechanism for the reaction between 1-methylpyrrole and dimethyl acetylenedicarboxylate (DMAD) has been studied using ab initio methods. Two alternative reaction pathways have been considered, both of which correspond to stepwise processes with initial, rate-determining formation of a common zwitterionic intermediate. This intermediate is formed by nucleophilic attack of the pyrrole ring to the carbon−carbon triple bond of DMAD. Closure of this intermediate (pathway A) affords a [4 + 2] cycloadduct, whereas intramolecular proton transfer (pathway B) affords a Michael adduct. The much larger potential energy barrier of the second step in pathway B relative to pathway A is respon…
Determination of Individual Gibbs Energies of Anion Transfer and Excess Gibbs Energies Using an Electrochemical Method Based on Insertion Electrochem…
2011
A method is presented to determine, individually and with minimal extra-thermodynamic assumptions, the Gibbs energy for anion transfer between two solvents using solid state electrochemistry of alkynyldiphosphine dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1, R = Fc; L2, R = C6H4Fc) and the heterometallic Au(I)–Cu(I) [{Au3Cu2(C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3, R = Fc; L4, R = C6H4Fc) cluster complexes containing ferrocenyl units. These compounds exhibit a well-defined, essentially reversible solid-state oxidation in contact with different electrolytes, based on ferrocenyl-centered oxidation processes involving anion insertion. Voltammetric data can be used for a direct measurement of…
Sodium bis(2-ethylhexyl)sulfosuccinate self-aggregation in vacuo: molecular dynamics simulation.
2010
Molecular dynamics (MD) simulations were conducted for systems in vacuo consisting of n AOT(-) anions (bis(2-ethylhexyl)sulfosuccinate ions) and n+/- 1 or n Na(+) ions up to n = 20. For n = 15, positively charged systems with Li(+), K(+), and Cs(+) cations were also considered. All systems were observed to form reverse micelle-like aggregates whose centre is occupied by cations and polar heads in a very compact solid-like way, while globally the aggregate has the form of an elongated and rather flat ellipsoid. Various types of statistical analyses were carried out on the systems to enlighten structural and dynamical properties including gyration radius, atomic pair correlation functions, at…
A Note on Riesz Bases of Eigenvectors of Certain Holomorphic Operator-Functions
2001
Abstract Operator-valued functions of the form A (λ) ≔ A − λ + Q(λ) with λ ↦ Q(λ)(A − μ)− 1 compact-valued and holomorphic on certain domains Ω ⊂ C are considered in separable Hilbert space. Assuming that the resolvent of A is compact, its eigenvalues are simple and the corresponding eigenvectors form a Riesz basis for H of finite defect, it is shown that under certain growth conditions on ‖Q(λ)(A − λ)− 1‖ the eigenvectors of A corresponding to a part of its spectrum also form a Riesz basis of finite defect. Applications are given to operator-valued functions of the form A (λ) = A − λ + B(λ − D)− 1C and to spectral problems in L2(0, 1) of the form −f″(x) + p(x, λ)f′(x) + q(x, λ)f(x) = λf(x…
Nonlinear diffusion in transparent media: the resolvent equation
2017
Abstract We consider the partial differential equation u - f = div ( u m ∇ u | ∇ u | ) u-f=\operatornamewithlimits{div}\biggl{(}u^{m}\frac{\nabla u}{|\nabla u|}% \biggr{)} with f nonnegative and bounded and m ∈ ℝ {m\in\mathbb{R}} . We prove existence and uniqueness of solutions for both the Dirichlet problem (with bounded and nonnegative boundary datum) and the homogeneous Neumann problem. Solutions, which a priori belong to a space of truncated bounded variation functions, are shown to have zero jump part with respect to the ℋ N - 1 {{\mathcal{H}}^{N-1}} -Hausdorff measure. Results and proofs extend to more general nonlinearities.