Ping-Pong Tunneling Reactions: Can Fluoride Jump at Absolute Zero?

Ashim Nandi, Adam Sucher, Sebastian Kozuch

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

In a recent study, Scheiner designed a double-germanium-based fluoride receptor that binds the halogen by means of strong tetrel bonds (Chem. Eur. J. 2016, 22, 18850). In this system the F binds to the germanium atoms in an asymmetric fashion, thereby producing a double-well potential in which the fluoride can jump from one germanium to the other as in a ping-pong game. Herein we prove through the use of computational tools that at cryogenic temperatures this rearrangement occurs by heavy-atom quantum mechanical tunneling. The inductive strength of the substituents and the polarity of the solvent can modify the barrier and the tunneling rate. But the strongest effect is observed upon modification of the geometry of the molecule by specific substitutions that affect the barrier width, the most critical factor in a tunneling mechanism. We postulate two experimental tests, one by microwave spectroscopy and one by cryogenic NMR spectroscopy, that can prove the predicted fluoride tunneling.

Original languageEnglish
Pages (from-to)16348-16355
Number of pages8
JournalChemistry - A European Journal
Volume24
Issue number61
DOIs
StatePublished - 2 Nov 2018

Keywords

  • computational chemistry
  • germanium
  • hole interactions
  • kinetics
  • quantum mechanical tunneling
  • tetrel bonds

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