The electronic properties of carbenes

Abstract

For carbenes as ambiphilic compounds there is no single scale for estimating their electron properties.Aim. To consider the known methods of estimating the electron-donating and electron-withdrawing properties of carbenes, first of all, created by the authors of the article, and show their possibilities in predicting the properties of carbenes.Materials and methods. The studies were performed using the DFT (B3LYP5/6-311G/RHF) method to estimate proton affinity, DFT (B3LYP5/3-21G/RHF and B3LYP5/3-21G/UHF) to determine chemical hardness and electronic indices.Results and discussion. The electronic properties of carbenes, including thermodynamic parameters, such as proton affinity (PA), chemical hardness η, and new electronic indices Ie, are discussed in the paper. With their help, the electron-donating and electron-withdrawing ability of a wide range of carbenes of both nucleophilic and electrophilic type has been estimated. It has been shown quantitatively that the electronic properties of carbenes depend both on the backbone of the molecule (for example, the type of the heterocyclic nucleus) and on substituents. The above data show the ways of regulating the structure of carbenes to achieve certain characteristics, which together with stability factors can be used in the design of structures for the synthesis and practical application.Conclusions. The author’s results of estimating proton affinity, chemical hardness and electronic indices for the design and use of carbene compounds are considered. Electronic indices have been shown to have some advantages over others for determining the nature (electron-donating and electron-withdrawing) of carbenes.