Aromaticity of six-membered nitro energetic compounds through molecular electrostatic potential, magnetic, electronic delocalization and reactivity-based indices.

The electron density depletion associated with π-hole at the ring center typical of energetic compounds was clearly revealed by the molecular electrostatic potential (ESP). In addition, the spatial arrangement of NO2 groups appears to affect the ESP value in the ring center, and therefore sensitivity to detonation. Indeed, for monocyclic nitrobenzene compounds with the same number of NO2 groups, the ESP value in the ring center decreases as the NO2 groups are more closely spaced. As expected, the central rings become less aromatic as NO2 groups are added. The MCI, PDI, PLR, NICSzz(1), FLU indices are all strongly correlated with the ESP values observed in the ring center of the set of nitrobenzenes. Aromaticity indices based on electron delocalization criteria appear to be very sensitive to small variations in aromaticity. Among magnetic-based indices, only NICSzz(1) is capable to predict small changes in aromaticity. The PLR index derived from conceptual DFT is quite relevant for predicting small variations in aromaticity. According to our results, the most suitable aromaticity index is not based on a single criterion, and that selecting it is more subtle. Therefore, it is important to combine information from several criteria to obtain a more complete description of the aromaticity of the studied compounds.

The effect of {O,N}=X⋯M={Ti,Zr,Hf} interactions on the sensitivity of CNO2 trigger bonds in FOX-7: Approach based on the QTAIM/EDA-NOCV analysis.

The local chemical reactivity of FOX-7 (1,1-diamino-2,2-nitroethylene, also known as DADNE from DiAminoDiNitroEthylene) was elucidated through a quantitative study of the electrostatic potential on the molecular surface, topological analysis based on Bader's theory, and the EDA-NOCV method. Unlike (O2N)2CC(NH2)H2N⋯Cp2MCH3+ complexes, which exhibit both σ-donor and π-acceptor features, the situation is different concerning the (H2N)2CC(NO2)(O)NO⋯Cp2MCH3+ complexes, where both charge transfers correspond to the σ-donation. The two charge transfers reinforce each other, resulting in increased stability for (H2N)2CC(NO2)(O)NO⋯Cp2MCH3+. This seems to strengthen the (H2N)2CC(NO2)(O)NO⋯M={Ti,Zr,Hf} bond, which may explain the high stability of (H2N)2CC(NO2)(O)NO⋯Cp2MCH3+ compared to (O2N)2CC(NH2)-H2N⋯Cp2MCH3+. Results from topological analysis revealed that the decreased sensitivity to decomposition of CNO2 bonds depends on the chemical nature of the interacting metal, and the best achievements are obtained for the Hf-based complex. Our results demonstrate that the interaction of M={Ti,Zr,Hf} with CNO2 is more favourable than that with CNH2, this specific action on the trigger bond may support the use of Metallocene Methyl Cations (MMC) as possible neutralisers.

Explaining the High Catalytic Activity in Bis(indenyl)methyl Zirconium Cation Using Combined EDA-NOCV/QTAIM Approach.

The main purpose of this study is to elucidate some discrepancies already observed in the catalytic activity values of some zirconocene methyl cations. The EDA-NOCV scheme was employed for a theoretical description of the interactions between an ethylene molecule and five catalysts of zirconocene methyl cation. The nature of the chemical interactions has been elucidated through the QTAIM topological analysis. The steric hindrance due to the ligands was evaluated qualitatively by means of an IRI-based analysis and quantitively through Fisher information. The findings prove that the indenyl ligand seems to favor the orbital interaction between the ethylene molecule and the metal centre of zirconocene methyl cation. Both electrostatic and orbital contributions play a crucial role in stabilising the studied complexes. Based on the NOCV deformation density contributions, the strongest orbital interaction is reached with the bis(indenyl)methyl zirconium cation, which is the only one exhibiting covalent interactions. Especially, the strong contribution of π-back donation (occurring from the occupied orbitals of the zirconium atom to the π* anti-bonding orbital of ethylene) may be a key to understand why this catalyst has a higher polymerisation yield than the other studied catalysts. This work suggests a perspective for predicting values of catalytic activity when theoretically designing novel catalysts of zirconocene type.

Theoretical investigation of the effect of O⋯M={Ti,Zr,Hf} interactions on the sensitivity of energetic N-nitro compounds.

This paper outlines the role of intermolecular interactions involving group 4 transition metals in stabilising the N-NO2 trigger bonds. Minimising sensitivity is the foremost priority in designing energetic compounds. A quantitative analysis with Molecular Electrostatic Potential (MEP) evidenced anomalies arising from the marked depletion of negative charge distribution of RDX and HMX. The Energy Decomposition Analysis with Natural Orbitals for Chemical Valence (EDA-NOCV) results reveal that the electrostatic and orbital contributions are the dominant factors driving the assembly of the M={Ti,Zr,Hf}-based complexes. Sensitivity of the N-NO2 trigger bonds is investigated by using the Quantum Theory of Atoms in Molecules (QTAIM). The QTAIM topological analysis showed that the O⋯M={Ti,Zr,Hf} interaction strengthens these trigger bonds, revealing an increased stability to decomposition. This effect is more marked in the Hf- and Zr-based complexes. Finally, the results based on Interaction Indicator Region (IRI) are fully consistent with those generated from QTAIM analysis.