Kinetic and Thermodynamic Evaluation of the Reversible N-Heterocyclic Carbene−Isothiocyanate Coupling Reaction: Applications in Latent Catalysis

Abstract

Using stopped flow and other spectroscopic techniques, the thermodynamic parameters of the coupling reaction between 1,3-dimesitylimidazolylidene and phenyl isothiocyanate were determined (H(o) = -96.1 kJ mol(-1) and ΔS(o) = -39.6 J mol(-1) K(-1)). On the basis of these data which indicated that the reaction was reversible (K(eq) = 5.94 × 10(14) M(-1) at 25 °C; k(f) = 252 M(-1) s(-1); k(r) = 4.24 × 10(-13) s(-1)), the adduct formed from the two aforementioned coupling partners was used as a latent catalyst to facilitate the [2 + 2 + 2] cyclotrimerization of phenyl isocyanate and the polymerization of DL-lactide.