Use of Molecular Electrostatic Potential at the Carbene Carbon as a Simple and Efficient Electronic Parameter of N-heterocyclic Carbenes

Abstract

Topographical analysis of the molecular electrostatic potential (MESP) has been carried out for a variety of N-heterocyclic carbenes at the B3LYP, BP86, and M05 levels of density functional theory (DFT) using a 6-311++G** basis set. The electron rich character of the carbene carbon is assessed in terms of the absolute minimum of the MESP at the carbene lone pair region (Vmin), as well as the MESP at the carbene nucleus (VC). A linear relationship is established between the VC and Tolman electronic parameter (TEP) which suggested the use of the former as a simple and efficient descriptor for the electron donating power of N-heterocyclic carbene ligands toward metal coordination. The Vmin of the carbene also showed good correlation with TEP. However, the deviation from linearity was higher than VC−TEP correlation, and the reason for this was attributed to the steric effect of N-substituents at the lone pair region. The greater coordinating power of N-heterocyclic carbenes over phosphines is explained on the basis of deeper Vmin values obtained for the former, and in fact even the Vmin of the least electron rich N-heterocyclic carbene is comparable to the highly electron rich phosphine ligands. Thus the MESP topographical approach presented herein offers quantification of the inherent electron donating power of a free N-heterocyclic carbene ligand.