Document Type

Article

Publication Date

7-21-2023

Abstract

The effect of fluoro substitution on the C–C bond activation of aromatic nitriles has been studied by reacting a variety of fluorinated benzonitriles with the nickel(0) fragment [Ni(dippe)] and by locating the reaction intermediates and transition-state structures on the potential energy surface by using density functional theory calculations with the [Ni(dmpe)] fragment (dippe = 1,2-bis(diisopropylphosphino)ethane, dmpe = 1,2-bis(dimethylphosphino)ethane). As in the previous reports, the reaction of fluorinated benzonitriles with the [Ni(dippe)] fragment initially formed an η2-nitrile complex, which then converted to the C–CN bond activation product. Thermodynamic parameters for the equilibrium between these complexes have been determined experimentally in both a polar (tetrahydrofuran) and a nonpolar (toluene) solvent for 3-fluoro- and 4-fluorobenzonitrile. The stability of the C–C bond activation products is shown to be strongly dependent on the number of ortho-F substituents (−6.6 kcal/mol per o-F) and only slightly dependent on the number of meta-F substituents (−1.8 kcal/mol per m-F).

Comments

Copyright © 2022 The Authors. Published by American Chemical Society. This publication is licensed under

CC-BY 4.0.

Creative Commons License

Creative Commons Attribution 4.0 International License
This work is licensed under a Creative Commons Attribution 4.0 International License.

Publication Title

Organometallics

DOI

https://doi.org/10.1021/acs.organomet.3c00275

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