Lanthanide induced paramagnetic shifts—derivation of equilibrium constants and absolute shifts in Eu(DPM)3 systems

Relationships between the magnitude of induced ¹H NMR shifts and the equilibrium conditions in solutions containing lanthanide shift reagents are discussed and applied to the shifts induced in several organic molecules by Eu(DPM)₃. Evidence that monoadduct formation is the predominant equilibrium in these solutions, and values of absolute shifts and equilibrium constants are reported. The results indicate that a contact mechanism makes the major contribution to the observed shifts in 4-methylpyridine. In the case of 2,4,6-trimethylpyridine the observed shifts are largely pseudocontact in origin.     

The role of partial saturation of the λ3 ladder in SF6 absorption under high power infrared laser excitation

A rate process model is developed to interpret the experimental results of Smith, Schmid, Tablas and Kompa on the time and intensity dependence of the infrared absorption of SF₆. In this model incoherent excitation of the λ₃ molecular mode by the processes of absorption and stimulated emission is followed by radiationless energy transfer from a maximum level to an inactive mode heatbath. This achieves control of the level population by an empirical transfer rate parameter. Good theoretical fits of the experiment absorption decays are obtained with values of approximately 0.1 ns.     

Metal‐Free Synthesis of Functional 1‐Substituted‐1,2,3‐Triazoles from Ethenesulfonyl Fluoride and Organic Azides

The boom in growth of 1,4‐disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the Cu^I‐catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1‐substituted‐1,2,3‐triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click‐inspired protocol for the synthesis of 1‐substituted‐1,2,3‐triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal‐free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1‐substituted‐1,2,3‐triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1‐substituted triazolium sulfonyl fluoride salts.     

Computational study of the oxidation and decomposition of dibenzofuran under atmospheric conditions

The atmospheric degradation of dibenzofuran (DF) initiated by OH addition has been studied by using density functional theory (B3LYP method). Site C1 in DF is predicted to be the favored site for OH addition, with a branching ratio of 0.61 to produce a DF-OH(1) adduct. The calculated reaction rate constant for OH addition to DF has been used to predict the atmospheric lifetime of DF to be 0.45 day. Three different modes of attack of O2 ((3)Sigma(g)) on DF-OH(1) have been examined. Abstraction of hydrogen gem to OH in DF-OH(1) by O2 ((3)Sigma(g)) (producing 1-dibenzofuranol I) and dioxygen addition in the three radical sites in cis and trans orientation (relative to the ispo-added OH) of the pi-delocalized electron system of DF-OH(1) are feasible under atmospheric conditions. The free energy of activation (at 298.15 K) for the formation of 1-dibenzofuranol is 15.1 kcal/mol with a free energy change of -36.3 kcal/mol, while the formation of DF-OH(1)-O2 adducts are endergonic by 9.2-21.8 kcal/mol with a 16.3-23.6 kcal/mol free energy of activation. On the basis of the calculated reaction rate constants, the formation of 1-dibenzofuranol is more important than the formation of DF-OH-O2 adducts. The results presented here are a first attempt to gain a better understanding of the atmospheric oxidation of dioxin-like compounds on a precise molecular basis.     

Quantum chemical and kinetic study of formation of 2-chlorophenoxy radical from 2-chlorophenol: unimolecular decomposition and bimolecular reactions with H, OH, Cl, and O2

This study investigates the kinetic parameters of the formation of the chlorophenoxy radical from the 2-chlorophenol molecule, a key precursor to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCCD/F), in unimolecular and bimolecular reactions in the gas phase. The study develops the reaction potential energy surface for the unimolecular decomposition of 2-chlorophenol. The migration of the phenolic hydrogen to the ortho-C bearing the hydrogen atom produces 2-chlorocyclohexa-2,4-dienone through an activation barrier of 73.6 kcal/mol (0 K). This route holds more importance than the direct fission of Cl or the phenolic H. Reaction rate constants for the bimolecular reactions, 2-chlorophenol + X --> X-H + 2-chlorophenoxy (X = H, OH, Cl, O2) are calculated and compared with the available experimental kinetics for the analogous reactions of X with phenol. OH reaction with 2-chlorophenol produces 2-chlorophenoxy by direct abstraction rather than through addition and subsequent water elimination. The results of the present study will find applications in the construction of detailed kinetic models describing the formation of PCDD/F in the gas phase.     

Quantum chemical investigation of formation of polychlorodibenzo-p-dioxins and dibenzofurans from oxidation and pyrolysis of 2-chlorophenol

Density functional theory (DFT) calculations have been used to obtain thermochemical parameters for formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) from the oxidation of 2-chlorophenol. Formation mechanisms of PCDD through radical-radical coupling have been investigated in detail. The sequence of 2-chlorophenoxy radical coupling has been studied. The formation of chlorinated bis keto dimers which results from cross coupling of 2-chlorophenoxy at the ortho carbon bearing hydrogen (a known direct route for PCDF formation) passes through a tight transition structure whose barrier is 9.4 kcal/mol (0 K). Three routes for the formation of the most abundant PCDD/PCDF species (viz., 4,6-dichlorodibenzofuran, 4,6-DCDF, and 1-monochlorodibenzo-p-dioxin, 1-MCDD) in oxidation and pyrolysis of 2-chlorophenol are discussed. In the case of 4,6-DCDF, formation through H or HO + keto-keto <==> H2 or H2O + keto-keto* <==> H2 or H2O + enol-keto* <==> H2 or H2O + 4,6-DCDF + HO is shown to be the preferred route. The other two routes proceed via closed shell processes (keto-keto <==> enol-keto <==> enol-enol <==> H2O + 4,6-DCDF) and (keto-keto <==> enol-keto <==> (H-,OH-) 4,6-DCDF <==> H2O + 4,6-DCDF). Results indicate that 1-MCDD should be the favored product in 2-chlorophenol pyrolysis in agreement with experimental findings. According to our results, tautomerization (inter-ring hydrogen transfer) and intra-annular displacement of HCl would not be competitive with paths deriving from H abstraction from the phenolic oxygen and the benzene ring followed by displacement of Cl in the formation of dibenzo-p-dioxin (DD) and 1-MCDD. The results presented here will assist in construction of detailed kinetic models to account for the formation of PCDD/PCDF from chlorophenols.     

Thermodynamic and transport properties of carbon dioxide from molecular simulation

Monte Carlo and molecular dynamics simulations have been used in order to test the ability of a three center intermolecular potential for carbon dioxide to reproduce literature experimental thermophysical values. In particular, both the shear viscosity under supercritical conditions and along the phase coexistence line, as well as the thermal conductivity under supercritical conditions, have been calculated. Together with the already reported excellent agreement for the phase coexistence densities, the authors find that the agreement with experimental values is, in general, good, except for the thermal conductivity at low density. Although extended versions of the model were employed, which include an explicit account of bending and vibrational degrees of freedom, a significant difference was still found with respect to the reported experimental value.     

Monte carlo simulation of self-assembled ordered hybrid materials

Lattice Monte Carlo simulations were performed to study the structure of hybrid organic-inorganic materials. Several cases were modeled where the composition corresponds to high surfactant concentration phases similar to that obtained from the synthesis of hybrid materials resulting from a phase separation. When using hybrid inorganic precursors, comparable to organosilicas, we observe that the organic segment is well mixed with the inorganic precursor and surfactant heads and no preferential location of the organic groups is observed. We show that the behavior of surfactant/hybrid precursor systems is analogous to those where co-surfactants or co-solvents are used, and that the lack of ordering in some cases can be explained by the change in solvent quality when using hybrid precursors. A comparison of structural characterization of the different phases using several tools, such as aggregate size distribution, density profiles, and pair radial distribution function is presented.     

Precise mass measurement of a double-stranded 500 base-pair (309 kDa) polymerase chain reaction product by negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) has been used to determine the mass of a double-stranded 500 base-pair (bp) polymerase chain reaction (PCR) product with an average theoretical mass of the blunt-ended (i.e. unadenylated) species of 308 859.35 Da. The PCR product was generated from the linearized bacteriophage Lambda genome which is a double-stranded template. Utilization of ethanol precipitation in tandem with a rapid microdialysis step to purify and desalt the PCR product was crucial to obtain a precise mass measurement. The PCR product (0.8 pmol/μL) was electrosprayed from a solution containing 75% acetonitrile, 25 mM piperidine, and 25 mM imidazole and was infused at a rate of 200 nL/min. The average molecular mass and the corresponding precision were determined using the charge-states ranging from 172 to 235 net negative charges. The experimental mass and corresponding precision (reported as the 95% confidence interval of the mean) was 309 406 +/- 27 Da (87 ppm). The mass accuracy was compromised due to the fact that the PCR generates multiple products when using Taq polymerase due to the non-template directed 3'-adenylation. This results in a mixture of three PCR products with nearly identical mass (i.e. blunt-ended, mono-adenylated and di-adenylated) with unknown relative abundances that were not resolved in the spectrum. Thus, the experimental mass will be a weighted average of the three species which, under our experimental conditions, reflects a nearly equal concentration of the mono- and di-adenylated species. This report demonstrates that precise mass measurements of PCR products up to 309 kDa (500 bp) can be routinely obtained by ESI-FTICR requiring low femtomole amounts. Copyright 1999 John Wiley & Sons, Ltd.     

Conformational analysis of dicarbonyl(methylcyclopentadienyl)(2-(diethylamino)-2-oxoethyl)iron(II): a spectroscopic and molecular mechanics study

A combination of NMR and IR spectroscopic techniques was used to examine the conformational preferences of the previously unreported oxaallyliron compound dicarbonyl(methylcyclopentadienyl)(2-(diethylamino)-2-oxoethyl)iron(II) (1). IR studies revealed that 1 existed in n-pentane solutions as an equilibrium between two or more exchanging conformers through a rotation about the Fe---C bond. An additional contribution to the conformational dynamics of 1 was identified due to the resonance component of the amide group. The resonance contribution manifested in the observed restricted rotation about the C---N amide bond. Molecular mechanics calculations were used to model the conformational processes. The calculations predicted that the resonance stabilized conformation was the energetically preferred structure of 1. This agrees with the experimental evidence that identified the influence of resonance on the conformation of 1.