School of Earth, Environmental, and Marine Sciences Faculty Publications and Presentations

Document Type

Article

Publication Date

11-21-2023

Abstract

A recent study of the oxidative addition of zerovalent Ni to the C–CN bond of F-substituted benzonitriles showed significantly increased stabilization of the C–CN oxidative addition products with o-F groups (−6.6 kcal/mol per o-F) compared to m-F groups (−1.8 kcal/mol per m-F). To answer the question of whether this is an o-F effect or an ortho effect, in this study the effect of CF3 and CH3 groups on the oxidative addition of the [Ni(dmpe)] fragment [dmpe = 1,2-bis(dimethylphosphino)ethane] to the C–CN bond of benzonitriles has been studied. A density functional theory study of the reaction pathway between η2-CN complexes and the C–CN oxidative addition products shows stabilization of the C–CN oxidative addition product with the electron-withdrawing CF3 group and destabilization with the electron-donating CH3 group in both tetrahydrofuran and toluene. There is a slightly larger ortho effect with CF3 (−7.4 kcal/mol) than with F. However, due to steric crowding, two o-CF3 groups did not show considerably more stabilization than one o-CF3 group. There is a linear relationship between Δ and the number of meta groups (2.0 kcal/mol stabilization per m-CF3 and 0.8 kcal/mol destabilization per m-CH3). On the basis of natural population analysis, as the C–CN bond becomes more polarized, the stability of the C–CN oxidative addition products with respect to the η2-CN complexes increases.

Publication Title

Inorganic Chemistry

DOI

https://doi.org/10.1021/acs.inorgchem.3c03065

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