Ortho-to-Fluorine Effect on the Sensitivity of (ACNC)Fe-C(sp2) Bond Dissociation Free Energies

Abstract

Ground-state DFT (density functional theory) studies were conducted on the bond strengths of iron-carbon bonds in (ACNC)Fe (pyridine bis(carbene)) complexes. These studies showed that the bond strengths increase with increasing ortho fluorine substitution. This selectivity is thermodynamic in nature and offers potential for novel selectivity in various C(sp2)- H functionalization reactions. The ortho fluorine effect is stronger on iron-carbon bonds than on the respective carbon-hydrogen bonds in a free arene.