Barrier DeltaG Research Articles

Nucleophilicities and Lewis basicities of imidazoles, benzimidazoles, and benzotriazoles

The kinetics of the reactions of some imidazoles, benzimidazoles and benzotriazoles with benzhydrylium ions (diarylcarbenium ions) have been studied photometrically in DMSO, acetonitrile, and aqueous solution at 20 degrees C. The resulting second-order rate constants have been used to determine the nucleophile-specific parameters N and s of these azoles according to the linear-free-energy relationship log k (20 degrees C) = s(N + E). With N = 11.47 (imidazole in acetonitrile), N = 10.50 (benzimidazole in DMSO), and N = 7.69 (benzotriazole in acetonitrile) these azoles are significantly less nucleophilic than previously characterized amines, such as DMAP (N = 14.95 in acetonitrile) and DABCO (N = 18.80 in acetonitrile). For some reactions of the 1-methyl substituted azoles with benzhydrylium ions equilibrium constants have been measured, which render a comparison of the Lewis basicities of these compounds. Substitution of the rate and equilibrium constants of these reactions into the Marcus equation yields the corresponding intrinsic barriers DeltaG(0)( not equal). From the ranking of DeltaG(0)( not equal) (imidazoles > pyridines > 1-azabicyclooctanes) one can derive that the reorganization energies for the reactions of imidazoles with electrophiles are significantly higher than those for the other amines and that imidazoles are less nucleophilic than pyridines and 1-azabicyclooctanes of comparable basicity.

Double Group Transfer Reactions: Role of Activation Strain and Aromaticity in Reaction Barriers

Double group transfer (DGT) reactions, such as the bimolecular automerization of ethane plus ethene, are known to have high reaction barriers despite the fact that their cyclic transition states have a pronounced in-plane aromatic character, as indicated by NMR spectroscopic parameters. To arrive at a way of understanding this somewhat paradoxical and incompletely understood phenomenon of high-energy aromatic transition states, we have explored six archetypal DGT reactions using density functional theory (DFT) at the OLYP/TZ2P level. The main trends in reactivity are rationalized using the activation strain model of chemical reactivity. In this model, the shape of the reaction profile DeltaE(zeta) and the height of the overall reaction barrier DeltaE( not equal)=DeltaE(zeta=zeta(TS)) is interpreted in terms of the strain energy DeltaE(strain)(zeta) associated with deforming the reactants along the reaction coordinate zeta plus the interaction energy DeltaE(int)(zeta) between these deformed reactants: DeltaE(zeta)=DeltaE(strain)(zeta)+DeltaE(int)(zeta). We also use an alternative fragmentation and a valence bond model for analyzing the character of the transition states.

Density Functional Investigation of the Water Exchange Reaction on the Gibbsite Surface

The water exchange reactions on the gibbsite surface have been investigated by density functional calculations (B3LYP/6-31G(d) level) combining the supermolecular model and PCM model in this paper, and the water exchange rate constants on the gibbsite surface have also been predicted. In the proposed reaction pathways, the clusters Al6(OH)18(H2O)6(0) and Al6(OH)12(H2O)12(6+) are used as the models of gibbsite surface and protonated gibbsite surface respectively to examine the effect of protonation of gibbsite surface on the water exchange rate constants. The activation energy barriers DeltaE(s) not equal to (aq) for Al6(OH)18(H2O)6(0) and Al6(OH)12(H2O)12(6+) are 28.6 and 27.2 kJ*mol-1, respectively. The reaction energies DeltaE(s) (aq) for Al6(OH)18(H2O)6(0) and Al6(OH)12(H2O)12(6+) are 2.9 and 14.4 kJ mol-1, respectively, indicating that hexacoordinate aluminum in the gibbsite surface is more stable. The log k(TST) for Al6(OH)18(H2O)6(0) and Al6(OH)12(H2O)12(6+) are 6.5 and 7.5 respectively, and the log k(ex) calculated by the given transmission coefficient for Al6(OH)18-(H2O)6(0) and Al6(OH)12(H2O)12(6+) are 2.4 and 3.4 respectively, indicating that the protonation of gibbsite surface promotes the water exchange reaction of gibbsite surface and accelerates the dissolution rate of gibbsite. The relationship between the calculated free energy and experimental rate constants was explored, and according to this relationship, the log k(ex) for Al6(OH)18(H2O)6(0) and Al6(OH)12(H2O)12(6+) are 2.5 and 3.1 respectively, close to the corresponding values calculated by the given transmission coefficient. The water exchange rate constant of gibbsite surface is close to those of K-MAl(12)(M = Al, Ga, and Ge) polyoxocations, but deviates from that of Al(H2O)6(3+), implying that the same reactions with similar structure have similar water exchange rate constants.

Domain Wall Switching: Optimizing the Energy Landscape

It has recently been suggested that exchange spring media offer a way to increase media density without causing thermal instability (superparamagnetism), by using a hard and a soft layer coupled by exchange. Victora has suggested a figure of merit xi=2E <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">b</sub> /mu <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">0</sub> m <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">s</sub> H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">sw</sub> , the ratio of the energy barrier to that of a Stoner-Wohlfarth system with the same switching field, which is 1 for a Stoner-Wohlfarth (coherently switching) particle and 2 for an optimal two-layer composite medium. A number of theoretical approaches have been used for this problem (e.g., various numbers of coupled Stoner-Wohlfarth layers and continuum micromagnetics). In this paper we show that many of these approaches can be regarded as special cases or approximations to a variational formulation of the problem, in which the energy is minimized for fixed magnetization. The results can be easily visualized in terms of a plot of the energy E as a function of magnetic moment m <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">z</sub> , in which both the switching field [the maximum slope of E(m <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">z</sub> )] and the stability (determined by the energy barrier DeltaE) are geometrically visible. In this formulation we can prove a rigorous limit on the figure of merit xi, which can be no higher than 4. We also show that a quadratic anistropy suggested by Suess comes very close to this limit.

Thermodynamic Origin of the Increased Rate of Hydrolysis of Phosphate and Phosphorothioate Esters in DMSO/Water Mixtures

The hydrolysis rates of the dianions of phosphate and phosphorothioate esters are substantially accelerated by the addition of polar aprotic solvents such as DMSO and acetonitrile. The activation barrier DeltaG is smaller due to a lower enthalpy of activation. The enthalpy of transfer of p-nitrophenyl phosphate (pNPP) and p-nitrophenyl phosphorothioate (pNPPT), from water to 0.6 (mol) aq DMSO (60 mol % water in DMSO) were measured calorimetrically. The enthalpies of activation for the hydrolysis reactions in the two solvents permitted the calculation of the enthalpy of transfer of the transition states. This transfer is thermodynamically favorable for both the reactants and the transition states but is more favorable for the transition states. In the case of pNPP, the enthalpy of transfer of the reactant is -23.9 kcal/mol, compared to -28.3 for the transition state. The difference is greater for pNPPT, where the enthalpy of transfer of the reactant is -23.2 kcal/mol and that for the transition state is -35.3. The results show that the reduced enthalpies of activation in both hydrolysis reactions arise not from a destabilization of the reactants in the mixed solvent, but from the fact that the enthalpy of transfer of the transition states to the mixed solvent is significantly more negative than the enthalpy of transfer of the reactants.

Dynamic 13C NMR studies of ligand exchange in linear (d10) silver(I) and gold(I) and square‐planar (d8) rhodium(I) homoleptic metal carbonyl cations in superacidic media

The dynamic CO exchange of the monovalent metal carbonyl cations [Ag(13CO)]+, [Au(13CO)2]+-Au(13CO) SO3F and [Rh(12CO)4-x(13CO)x]+ (x < or = 1) in superacidic solutions was studied by variable-temperature 13C NMR methods. The exchange rates are strongly dependent on the acidity of the solvent, the concentration of metal carbonyl cations and temperature. Whereas a suitable exchange rate of the Ag(I) system is only accessible in magic acid (HSO3F-SbF5), the more stable Au(I) and Rh(I) systems were studied in the less acidic fluorosulfuric acid. Selected solutions of Ag(I), Rh(I) and Au(I) yielded activation barriers deltaG* of 42.7, 43.5, and 56.2 kJ mol(-1) respectively.

Peralkynylated buta-1,2,3-trienes: exceptionally low rotational barriers of cumulenic C=C bonds in the range of those of peptide C--N bonds.

A variety of 1,1,4,4-tetraal kynylbutatrienes and 1,4-dialkynylbutatrienes was synthezized by dimerization of the corresponding gem-dibromoolefins. Both (1)H and (13)C NMR spectroscopy indicated that the di- and tetraalkynylated butatrienes are formed as a mixture of cis and trans isomers. Variable temperature NMR studies evidenced a facile cis-trans isomerization, thus preventing the separation of these isomers by gravity or high-performance liquid chromatography (HPLC). For 1,1,4,4-tetraalkynylbutatrienes, the activation barrier deltaG( not equal ) was measured by magnetization transfer to be around 20 kcal mol(-1), in the range of the barrier for internal rotation about a peptide bond. Unlike the tetraalkynylated [3]cumulenes, 1,4-dialkynylbutatrienes are more difficult to isomerize and could, in one case, be obtained isomerically pure. Based on experimental data, the rotational barrier DeltaG( not equal ) for 1,4-dialkynylbutatrienes is estimated to be around 25 kcal mol(-1). The hypothesis of a stabilizing effect of the four alkynyl substituents on the proposed but-2-yne-1,4-diyl singlet diradical transition state of this cis-trans isomerization is further supported by a computational study.

Donor-acceptor (electronic) coupling in the precursor complex to organic electron transfer: intermolecular and intramolecular self-exchange between phenothiazine redox centers.

Intermolecular electron transfer (ET) between the free phenothiazine donor (PH) and its cation radical (PH*+) proceeds via the [1:1] precursor complex (PH)(2)*+ which is transiently observed for the first time by its diagnostic (charge-resonance) absorption band in the near-IR region. Similar intervalence (optical) transitions are also observed in mixed-valence cation radicals with the generic representation: P(br)P*+, in which two phenothiazine redox centers are interlinked by p-phenylene, o-xylylene, and o-phenylene (br) bridges. Mulliken-Hush analysis of the intervalence (charge-resonance) bands afford reliable values of the electronic coupling element H(IV) based on the separation parameters for (P/P*+) centers estimated from some X-ray structures of the intermolecular (PH)(2)*+ and the intramolecular P(br)P*+ systems. The values of H(IV), together with the reorganization energies lambda derived from the intervalence transitions, yield activation barriers DeltaG(ET)() and first-order rate constants k(ET) for electron-transfer based on the Marcus-Hush (two-state) formalism. Such theoretically based values of the intrinsic barrier and ET rate constants agree with the experimental activation barrier (E(a)) and the self-exchange rate constant (k(SE)) independently determined by ESR line broadening measurements. This convergence validates the use of the two-state model to adequately evaluate the critical electronic coupling elements between (P/P*+) redox centers in both (a) intermolecular ET via the precursor complex and (b) intramolecular ET within bridged mixed-valence cation radicals. Important to intermolecular ET mechanism is the intervention of the strongly coupled precursor complex since it leads to electron-transfer rates of self-exchange that are 2 orders of magnitude faster (and activation barrier that is substantially lower) than otherwise predicted solely on the basis of Marcus reorganization energy.

Determination of the enantiomerization barrier of thalidomide by dynamic capillary electrokinetic chromatography.

Enantioselective chromatographic methods, representing the most commonly used techniques for the determination of enantiomeric ratios, can also be used for the evaluation of stereochemical integrity. In the present study, dynamic capillary electrokinetic chromatography (DEKC) was employed to determine the enantiomerization barrier of thalidomide. In the presence of the chiral mobile phase additive carboxymethyl-beta-cyclodextrin, the interconverting enantiomers of thalidomide produced characteristic elution profiles exhibiting plateaus and/or peak broadening between 25 and 55 degrees C at pH 8. To obtain the enantiomerization barrier of thalidomide from experimental data, the fast and efficient simulation program ChromWin was used to simulate the experimental interconversion profiles and to obtain the apparent rate constants k1app(T). Additionally, these values were compared with the novel approximation function for the direct calculation of enantiomerization barriers from chromatographic parameters of elution profiles. From the rate constants k1app(T) of temperature-dependent measurements the kinetic activation parameters deltaG(T)#,deltaH#, and deltaS# of the enantiomerization of thalidomide were obtained. At 25 degrees C, the enantiomerization barrier deltaG# was determined to be 102 +/- 1 kJ/mol at pH 8 in the dynamic electrokinetic chromatographic experiment.

2+3] Cycloaddition of Ethylene to Transition Metal Oxo Compounds. Analysis of Density Functional Results by Marcus Theory

Density functional results on the [2+3] cycloaddition of ethylene to various transition metal complexes MO(3)(q) and LMO(3)(q) (q = -1, 0, 1) with M = Mo, W, Mn, Tc, Re, and Os and various ligands L = Cp, CH(3), Cl, and O show that the corresponding activation barriers DeltaE(double dagger) depend in quadratic fashion on the reaction energies DeltaE(0) as predicted by Marcus theory. A thermoneutral reaction is characterized by the intrinsic reaction barrier DeltaE(0) of 25.1 kcal/mol. Both ethylene [2+3] cycloaddition to an oxo complex and the corresponding homolytic M-O bond dissociation are controlled by the reducibility of the transition metal center. Indeed, from the easily calculated M-O bond dissociation energy of the oxo complex one can predict the reaction energy DeltaE(0) and hence, by Marcus theory, the corresponding activation barrier DeltaE. This allows a systematic representation of more than 25 barriers of [2+3] cycloaddition reactions that range from 5 to 70 kcal/mol.

Four Enantiomerization Routes of 1,2,2-Trimesitylvinyl Acetate. Enantioselective Liquid Chromatography of (E)- and (Z)-2-m-Methoxymesityl-1,2-dimesitylvinyl Acetates.

The vinyl propellers (E)- and (Z)-2-m-methoxymesityl-1,2-dimesitylvinyl acetates (3c and 3d) were prepared and their geometries assigned. The stereoisomerization barriers of the trimesityl vinyl acetate system were determined by DNMR and by enantioselective LC resolution and polarimetric monitoring of the behavior of the two diastereomeric racemates of 3c and 3d. Combined with data for trimesitylvinyl-OAc 3a and its 1-m-methoxymesityl analogue 3b, the following order of barriers DeltaG() is obtained: alphabeta-2-ring flip > alphabeta'-2-ring flip > betabeta'-2-ring flip > alphabetabeta'-3-ring flip (the threshold enantiomerization barrier). This order which differs from the previously found orders for trimesitylvinyl-X, X = H, OPr-i was rationalized and discussed.