Boron Tunneling in the “Weak” Bond-Stretch Isomerization of N−B Lewis Adducts

Ashim Nandi, Naziha Tarannam, Daniela Rodrigues Silva, Célia Fonseca Guerra, Trevor A. Hamlin, Sebastian Kozuch*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Some nitrile-boron halide adducts exhibit a double-well potential energy surface with two distinct minima: a “long bond” geometry (LB, a van der Waals interaction mostly based on electrostatics, but including a residual charge transfer component) and a “short bond” structure (SB, a covalent dative bond). This behavior can be considered as a “weak” form of bond stretch isomerism. Our computations reveal that complexes RCN−BX3 (R=CH3, FCH2, BrCH2, and X=Cl, Br) exhibit a fast interconversion from LB to SB geometries even close to the absolute zero thanks to a boron atom tunneling mechanism. The computed half-lives of the meta-stable LB compounds vary between minutes to nanoseconds at cryogenic conditions. Accordingly, we predict that the long bond structures are practically impossible to isolate or characterize, which agrees with previous matrix-isolation experiments.

Original languageEnglish
Pages (from-to)1857-1862
Number of pages6
JournalChemPhysChem
Volume22
Issue number18
Early online date10 Jul 2021
DOIs
Publication statusPublished - 15 Sep 2021

Bibliographical note

Funding Information:
This research was supported by the Israeli Science Foundation (grant no. 841/19) and the Netherlands Organization for Scientific Research (NWO). A.N. and N.T. acknowledges the Kreitman Graduate School of Advanced Studies for the Negev-Tsin and the mid-way Negev fellowships.

Funding Information:
This research was supported by the Israeli Science Foundation (grant no. 841/19) and the Netherlands Organization for Scientific Research (NWO). A.N. and N.T. acknowledges the Kreitman Graduate School of Advanced Studies for the Negev‐Tsin and the mid‐way Negev fellowships.

Publisher Copyright:
© 2021 Wiley-VCH GmbH

Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.

Keywords

  • bond stretch isomerism
  • dative bond
  • heavy-atom tunneling
  • kinetic isotope effect
  • Lewis adduct

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