Unveiling the Intramolecular Ionic Diels-Alder Reactions within the Molecular Electron Density Theory

The intramolecular ionic Diel-Alder (IIDA) reactions of two dieniminiums have been studied within the Molecular Electron Density Theory (MEDT) at the B97XD/6-311G(d,p) computational level. ELF topological analysis of dieniminiums shows that its electronic structure can been seen as the sum of those of butadiene and ethaniminium. The superelectrophilic character of dieniminiums accounts for the high intramolecular global electron density transfer taking place between the diene and iminium frameworks at the transition state structures (TSs) of these IIDA reactions. The activation enthalpy associated to the IIDA reaction of the experimental dieniminium, 8.7 kcal·mol-1, is closer to that of the ionic Diels-Alder (I-DA) reaction between butadiene and ethaniminium, 9.3 kcal·mol-1. However, the activation Gibbs free energy of the IIDA reaction is 12.7 kcal·mol-1 lower than that of the intermolecular I-DA reaction. The strong exergonic character of the IIDA reaction, higher than 17 kcal·mol-1, makes the reaction irreversible. These IIDA reactions present a total re/exo and si/endo diastereoselectivity, which is controlled by the most favourable chair conformation of the tetramethylene chain. Electron localization function (ELF) topological analysis of the single bond formation indicates that these IIDA reactions take place through a non-concerted two-stage one-step mechanism. Finally, ELF and atoms-in-molecules (AIM) topological analyses of the TS associated to inter and intramolecular processes show the great similitude among them.

Unveiling the Ionic Diels–Alder Reactions within the Molecular Electron Density Theory

The ionic Diels–Alder (I-DA) reactions of a series of six iminium cations with cyclopentadiene have been studied within the Molecular Electron Density Theory (MEDT). The superelectrophilic character of iminium cations, ω > 8.20 eV, accounts for the high reactivity of these species participating in I-DA reactions. The activation energies are found to be between 13 and 20 kcal·mol−1 lower in energy than those associated with the corresponding Diels–Alder (DA) reactions of neutral imines. These reactions are low endo selective as a consequence of the cationic character of the TSs, but highly regioselective. Solvents have poor effects on the relative energies, and an unappreciable effect on the geometries. In acetonitrile, the activation energies increase slightly as a consequence of the better solvation of the iminium cations than the cationic TSs. Electron localization function (ELF) topological analysis of the bonding changes along the I-DA reactions shows that they are very similar to those in polar DA reactions. The present MEDT study establishes that the global electron density transfer (GEDT) taking place at the TSs of I-DA reactions, and not steric (Pauli) repulsions such as have been recently proposed, are responsible for the features of these types of DA reactions.

Unveiling the Ionic Diels-Alder Reactions within the Molecular Electron Density Theory

The ionic Diels-Alder (I-DA) reactions of a series of six iminium cations with cyclopentadiene have been studied within the Molecular Electron Density Theory (MEDT). The superelectrophilic character of iminium cations,  > 8.20 eV, accounts for the high reactivity of these species participating in I-DA reactions. The activation energies are found between 13 and 20 kcal·mol-1 lower in energy than those associated to the corresponding Diels-Alder (DA) reactions of neutral imines. These reactions are low endo selective as a consequence of the cationic character of the TSs, but highly regioselective. Solvents have poor effects on the relative energies, and an unappreciable effect in the geometries. In dichloromethane the activation energies increase slightly as a consequence of the better solvation of the iminium cations than the cationic TSs. ELF topological analysis of the bonding changes along the I-DA reactions shows that they are very similar to those in polar DA reactions. The present MEDT study makes it possible establishing that the global electron density transfer (GEDT) taking place at the TSs of I-DA reactions, and not steric (Pauli) repulsions such as have been recently proposed, are responsible for the features of these type of DA reactions.

Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory

The [3+2] cycloaddition (32CA) reactions of strongly nucleophilic norbornadiene (NBD), with simplest diazoalkane (DAA) and three DAAs of increased electrophilicity, have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G (d,p) computational level. These pmr-type 32CA reactions follow an asynchronous one-step mechanism with activation enthalpies ranging from 17.7 to 27.9 kcal·mol−1 in acetonitrile. The high exergonic character of these reactions makes them irreversible. The presence of electron-withdrawing (EW) substituents in the DAA increases the activation enthalpies, in complete agreement with the experimental slowing-down of the reactions, but contrary to the Conceptual DFT prediction. Despite the nucleophilic and electrophilic character of the reagents, the global electron density transfer at the TSs indicates rather non-polar 32CA reactions. The present MEDT study establishes the depopulation of the N–N–C core in this series of DAAs with the increase of the EW character of the substituents present at the carbon center is responsible for the experimentally found deceleration.

Unveiling the regioselective synthesis of antiviral 5-isoxazol-5-yl-2'deoxyuridines with a molecular electron density theory perspective

The regioselective synthesis of a potent antiviral sugar nucleoside isoxazole analogue from the [3+2] cycloaddition (32CA) reaction of aceto-nitrile-N-oxide (ANO) and acetyl-protected 5-ethynyl-2?-deoxyuridine (EDU) has been studied at MPWB1K/6-311G(d,p) level within the molecular electron density theory (MEDT) perspective. ANO is classified as a zwitterionic species devoid of any pseudoradical or carbenoid center from the electron localization function (ELF) analysis. The ortho regioisomer is energetically preferred over the meta one by the activation enthalpy of 21.7-24.3 kJ mol-1, suggesting complete regioselectivity in agreement with the experiment. The activation enthalpy increases from 53.9 kJ mol-1 in gas phase to 71.5 kJ mol-1 in water suggesting more facile reaction in low polar solvents. The minimal global electron density transfer (GEDT) at the TSs suggests non-polar character and the formation of new covalent bonds has not been started at the located TSs showing non-covalent intermolecular interactions from Atoms-in-Molecules (AIM) study and in the Independent Gradient Model (IGM) isosurfaces. The AIM analysis shows more accumulation of electron density at the C-C interacting region relative to the C-O one, and earlier C-C bond formation is predicted from the bonding evolution theory (BET) study.

Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory

The [3+2] cycloaddition (32CA) reactions of strongly nucleophilic norbornadiene (NBD) with simplest diazoalkane (DAA) and three DAAs of increased electrophilicity have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d,p) computational level. These pmr-type 32CA reactions follow an asynchronous one-step mechanism with activation enthalpies ranging from 17.7 to 27.9 kcal·mol-1 in acetonitrile. The high exergonic character of these reactions makes them irreversible. The presence of electron-withdrawing (EW) substituents in the DAA increases the activation enthalpies, in complete agreement with the experimental slowing-down of the reactions, but contrary to the Conceptual DFT prediction. Despite the nucleophilic and electrophilic character of the reagents, the global electron density transfer at the TSs indicates rather non-polar 32CA reactions. The present MEDT study allows establishing that the depopulation of the NNC core in this series of DAAs with the increase of the EW character of the substituents present at the carbon center is responsible for the experimentally found deceleration.

Accurate equilibrium structure of 3-aminophthalimide from gas electron diffraction and coupled-cluster computations and diverse structural effects due to electron density transfer

The accurate equilibrium structure determination enables the observation of fine structural effects in 3-aminophthalimide due to the electron density transfer.

Dzyaloshinskii–Moriya Coupling in 3d Insulators

We present an overview of the microscopic theory of the Dzyaloshinskii–Moriya (DM) coupling in strongly correlated 3d compounds. Most attention in the paper centers around the derivation of the Dzyaloshinskii vector, its value, orientation, and sense (sign) under different types of the (super)exchange interaction and crystal field. We consider both the Moriya mechanism of the antisymmetric interaction and novel contributions, in particular, that of spin–orbital coupling on the intermediate ligand ions. We have predicted a novel magnetic phenomenon, weak ferrimagnetism in mixed weak ferromagnets with competing signs of Dzyaloshinskii vectors. We revisit a problem of the DM coupling for a single bond in cuprates specifying the local spin–orbital contributions to the Dzyaloshinskii vector focusing on the oxygen term. We predict a novel puzzling effect of the on-site staggered spin polarization to be a result of the on-site spin–orbital coupling and the cation-ligand spin density transfer. The intermediate ligand nuclear magnetic resonance (NMR) measurements are shown to be an effective tool to inspect the effects of the DM coupling in an external magnetic field. We predict the effect of a strong oxygen-weak antiferromagnetism in edge-shared CuO 2 chains due to uncompensated oxygen Dzyaloshinskii vectors. We revisit the effects of symmetric spin anisotropy directly induced by the DM coupling. A critical analysis will be given of different approaches to exchange-relativistic coupling based on the cluster and the DFT (density functional theory) based calculations. Theoretical results are applied to different classes of 3d compounds from conventional weak ferromagnets ( α -Fe 2 O 3 , FeBO 3 , FeF 3 , RFeO 3 , RCrO 3 , ...) to unconventional systems such as weak ferrimagnets (e.g., RFe 1 - x Cr x O 3 ), helimagnets (e.g., CsCuCl 3 ), and parent cuprates (La 2 CuO 4 , ...).

Quantum-chemical studies of rutile nanoparticles toxicity I. Defect-free rod-like model clusters

Using the semiempirical PM6 method, structures of a rod-like [Ti40O124H81]7– model cluster and of [Ti40O124H81Cu]5– with Cu2+ coordinated at various sites were optimized in order to assess the toxicity of rutile nanoparticles. If the relative toxicity of individual Ti centers in rod-like rutile nanoparticles can be evaluated by the electron density transfer to a Cu2+ probe, its maximal values can be ascribed to the pentacoordinated corner and hexacoordinated edge Ti centers with three Ti—OH bonds. However, these centers exhibit the least negative interaction energies which can be compensated by the significantly better accessibility of the corner Ti center compared with that of the remaining ones. Ti centers with the most negative interaction energy parameters exhibit the lowest extent of electron density transfer to a Cu2+ probe. Rutile nanoparticles destruction starts at pentacoordinated Ti face centers.