Comment on "The Nature of Chalcogen‐Bonding‐Type Tellurium–Nitrogen Interactions": Fixing the Description of Finite‐Temperature Effects Restores the Agreement Between Experiment and Theory. Issue 24 (7th May 2021)

• Record Type: Journal Article
• Authors: Mewes, Jan‐Michael; Hansen, Andreas; Grimme, Stefan
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 24(2021)
• Page Start: 13144
• Page End: 13149
• Publication Date: 2021-05-07
• Subjects: finite-temperature effects -- gas phase -- molecular dynamics -- non-covalent interactions -- tellurium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202102679
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Mitzel and co‐workers recently presented an intriguing molecule displaying a tellurium–nitrogen interaction. Structural data obtained in the solid and in gas phase indicated a large increase of the Te–N equilibrium distance r e from 2.64 to 2.92 Å, respectively. Although some DFT calculations appear to support the large r e in gas phase, we argue that the lions share of the increase is due to an incomplete description of finite‐temperature effects in the back‐corrected experimental data. This hypothesis is based on high‐level coupled‐cluster (CC) and periodic DFT calculations, which consistently point towards a much smaller r e in the isolated molecule. Further support comes through MD simulations with a tuned GFN2‐xTB Hamiltonian: Calibrated against a CC reference, these show a six‐times larger influence of temperature than with the originally used GFN1‐xTB. Taking this into account, the back‐corrected r e in gas phase becomes 2.67±0.08 Å, in good agreement with high‐level CC theory and most DFT methods. Abstract : An intriguing molecule displaying a tellurium–nitrogen interaction has been recently presented. Structural data indicated a large increase of the Te−N equilibrium distance from 2.64 Å in the solid to 2.92 Å in gas phase. We show that the lions share of the increase is due to an incomplete description of finite‐temperature effects in the back‐corrected experimental data.