Quantification of Noncovalent Interactions in Azide–Pnictogen, –Chalcogen,and –Halogen Contacts |
| |
Authors: | Markus Bursch Lukas Kunze Dr Amol M Vibhute Dr Andreas Hansen Prof?Dr Kana M Sureshan Dr Peter G Jones Prof?Dr Stefan Grimme Prof?Dr Daniel B Werz |
| |
Institution: | 1. Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstraße 4, 53115 Bonn, Germany;2. Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany;3. School of Chemistry, IISER Thiruvananthapuram, Kerala, 695551 India;4. Technische Universität Braunschweig, Institut für Anorganische und Analytische Chemie, Hagenring 30, 38106 Braunschweig, Germany |
| |
Abstract: | The noncovalent interactions between azides and oxygen-containing moieties are investigated through a computational study based on experimental findings. The targeted synthesis of organic compounds with close intramolecular azide–oxygen contacts yielded six new representatives, for which X-ray structures were determined. Two of those compounds were investigated with respect to their potential conformations in the gas phase and a possible significantly shorter azide–oxygen contact. Furthermore, a set of 44 high-quality, gas-phase computational model systems with intermolecular azide–pnictogen (N, P, As, Sb), –chalcogen (O, S, Se, Te), and –halogen (F, Cl, Br, I) contacts are compiled and investigated through semiempirical quantum mechanical methods, density functional approximations, and wave function theory. A local energy decomposition (LED) analysis is applied to study the nature of the noncovalent interaction. The special role of electrostatic and London dispersion interactions is discussed in detail. London dispersion is identified as a dominant factor of the azide–donor interaction with mean London dispersion energy-interaction energy ratios of 1.3. Electrostatic contributions enhance the azide–donor coordination motif. The association energies range from ?1.00 to ?5.5 kcal mol?1. |
| |
Keywords: | azides density functional calculations local energy decomposition London dispersion noncovalent interactions |
|
|