Olefin Metathesis Catalyzed by a Hoveyda–Grubbs-like Complex Chelated to Bis(2-mercaptoimidazolyl) Methane: A Predictive DFT Study

Although highly selective complexes for the cross-metathesis of olefins, particularly oriented toward the productive metathesis of Z-olefins, have been reported in recent years, there is a constant need to design and prepare new and improved catalysts for this challenging reaction. In this work, guided by density functional theory (DFT) calculations, the performance of a Ru-based catalyst chelated to a sulfurated pincer in the olefin metathesis was computationally assessed. The catalyst was designed based on the Hoveyda–Grubbs catalyst (SIMes)Cl2Ru(═CH–o–OiPrC6H4) through the substitution of chlorides with the chelator bis(2-mercaptoimidazolyl)methane. The obtained thermodynamic and kinetic data of the initiation phase through side- and bottom-bound mechanisms suggest that this system is a versatile catalyst for olefin metathesis, as DFT predicts the highest energy barrier of the catalytic cycle of ca. 20 kcal/mol, which is comparable to those corresponding to the Hoveyda–Grubbs-type catalysts. Moreover, in terms of the stereoselectivity evaluated through the propagation phase in the metathesis of propene–propene to 2-butene, our study reveals that the Z isomer can be formed under a kinetic control. We believe that this is an interesting outcome in the context of future exploration of Ru-based catalysts with sulfurated chelates in the search for high stereoselectivity in selected reactions.