Transition metal carbene chemistry7: Nucleophilic substitution reactions of imidazolide and benzimidazolide ions with Fischer carbene complexes in MeOH

Rate constants for the nucleophilic substitution reactions of imidazolide (IZ−) and benzimidazolide (BIZ−) ions with 4-Cr-Z and 5 in MeOH at 25 °C are reported and Hammett ρ values are evaluated to be 1.50 ± 0.10 and 1.51 ± 0.08 for 4-Cr-Z-IZ− and 4-Cr-Z-BIZ− reactions, respectively. The comparable reactivity and also almost identical ρ values for these reactions indicate that there is no difference in sensitivity towards electronic effects due to slightly bigger size of BIZ− over IZ− and bond formation at the transition states are equally progressed. The higher ρ values for these reactions compared to those with a wide range of nucleophiles may arise mainly due to lower polarity of the solvent MeOH which enhances the requirement for stabilization of the negative charge in the transition state by the Z-substituents.

Graphical abstractRate constants for the nucleophilic substitution reactions of imidazolide and benzimidazolide ions with 4-Cr-Z and 5 in MeOH at 25 °C are reported. The Hammett ρ values are 1.50 ± 0.10 and 1.51 ± 0.08 for 4-Cr-Z-IZ− and 4-Cr-Z-BIZ− reactions, respectively. The comparable reactivity and also almost identical ρ values indicate that there is no difference in reactivity due to slightly bigger size of benzimidazolide over imidazolide ions and bond formation at the transition states are equally progressed.Figure optionsDownload full-size imageDownload as PowerPoint slide