Exploring Unconventional σ-Hole Interactions: Computational Insights into the Interaction of XeO with Non-Aromatic Coordinating Solvents.

Chemphyschem

Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 411008, India.

Published: March 2024

AI Article Synopsis

  • - The study explores the interactions of xenon oxide (XeO) with various non-aromatic solvents to control its explosiveness and shock sensitivity, using density functional theory (DFT) calculations on twenty-six solvents.
  • - The top ten solvents were analyzed through multiple computational methods, revealing significant interactions such as C-H...O bonds, and examining the amphoteric behavior of XeO with potential Lewis base donors.
  • - Among the solvents studied, hexamethylphosphoramide (HMPA), N,N'-dimethylpropyleneurea (DMPU), and tetramethylethylenediamine (TMEDA) were identified as the three strongest candidates for forming stable adducts with XeO. *

Article Abstract

In order to control the explosiveness and shock sensitivity of XeO , we have investigated its plausible interaction with various non-aromatic coordinating solvents, serving as potential Lewis base donors, through density functional theory (DFT) calculations. Out of twenty six such solvents, the top ten were thus identified and then thoroughly examined by employing various computational tools such as the mapping of the electrostatic potential surface (MESP), Wiberg bond indices (WBIs), non-covalent interaction (NCI) plots, Bader's theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, and the energy decomposition analysis (EDA). The amphoteric nature of XeO was also explored by investigating the extent of back donation from the lone pair of Xe to the antibonding orbital of the donating atom/group of the solvent molecules. The C-H…O interactions were also found to be a contributing factor in the stabilization of these adducts. Although these aerogen-bonding interactions were found to be predominantly electrostatic, significant contributions from the orbital contributions, as well as dispersion interactions, were observed. The top three non-aromatic solvents (among the twenty six studied) which form the strongest adducts with XeO are proposed to be hexamethylphosphoramide (HMPA), N,N'-dimethylpropyleneurea (DMPU) and tetramethylethylenediamine (TMEDA).

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http://dx.doi.org/10.1002/cphc.202300908DOI Listing

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Exploring Unconventional σ-Hole Interactions: Computational Insights into the Interaction of XeO with Non-Aromatic Coordinating Solvents.

Chemphyschem

March 2024

Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 411008, India.

In order to control the explosiveness and shock sensitivity of XeO , we have investigated its plausible interaction with various non-aromatic coordinating solvents, serving as potential Lewis base donors, through density functional theory (DFT) calculations. Out of twenty six such solvents, the top ten were thus identified and then thoroughly examined by employing various computational tools such as the mapping of the electrostatic potential surface (MESP), Wiberg bond indices (WBIs), non-covalent interaction (NCI) plots, Bader's theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, and the energy decomposition analysis (EDA). The amphoteric nature of XeO was also explored by investigating the extent of back donation from the lone pair of Xe to the antibonding orbital of the donating atom/group of the solvent molecules.

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